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

NASA Astrophysics Data System (ADS)

Kim, Yong-Hyun; Kim, Ki-Hyun

2015-07-01

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

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.

Biodegradation of high-molecular-weight polycyclic aromatic hydrocarbons under anaerobic conditions: Overview of studies, proposed pathways and future perspectives.

PubMed

Nzila, Alexis

2018-05-07

The biodegradation of low- and high-molecular-weight polycyclic aromatic hydrocarbons (PAHs) (LWM-PAHs and HMW-PAHs, respectively) has been studied extensively under aerobic conditions. Molecular O 2 plays 2 critical roles in this biodegradation process. O 2 activates the aromatic rings through hydroxylation prior to ring opening and serves as a terminal electron acceptor (TEA). However, several microorganisms have devised ways of activating aromatic rings, leading to ring opening (and thus biodegradation) when TEAs other than O 2 are used (under anoxic conditions). These microorganisms belong to the sulfate-, nitrate-, and metal-ion-reducing bacteria and the methanogens. Although the anaerobic biodegradation of monocyclic aromatic hydrocarbons and LWM-PAH naphthalene have been studied, little information is available about the biodegradation of HMW-PAHs. This manuscript reviews studies of the anaerobic biodegradation of HMW-PAHs and identifies gaps that limit both our understanding and the efficiency of this biodegradation process. Strategies that can be employed to overcome these limitations are also discussed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Surface water polycyclic aromatic hydrocarbons (PAH) in urban areas of Nanjing, China.

PubMed

Wang, Chunhui; Zhou, Shenglu; Wu, Shaohua; Song, Jing; Shi, Yaxing; Li, Baojie; Chen, Hao

2017-10-01

The concentration, sources and environmental risks of polycyclic aromatic hydrocarbons (PAHs) in surface water in urban areas of Nanjing were investigated. The range of ∑ 16 PAHs concentration is between 4,076 and 29,455 ng/L, with a mean of 17,212 ng/L. The composition of PAHs indicated that 2- and 3-ring PAHs have the highest proportion in all PAHs, while the 5- and 6-ring PAHs were the least in proportion. By diagnostic ratio analysis, combustion and petroleum were a mixture input that contributed to the water PAH in urban areas of Nanjing. Positive matrix factorization quantitatively identified four factors, including coke oven, coal combustion, oil source, and vehicle emission, as the main sources. Toxic equivalency factors of BaP (BaP eq ) evaluate the environmental risks of PAHs and indicate the PAH concentration in surface water in urban areas of Nanjing had been polluted and might cause potential environmental risks. Therefore, the PAH contamination in surface water in urban areas of Nanjing should draw considerable attention.

Photooxidation products of polycyclic aromatic compounds containing sulfur.

PubMed

Bobinger, Stefan; Andersson, Jan T

2009-11-01

Photooxidation of crude oil components is an important process that removes pollutants from the environment. Polycyclic aromatic compounds (PACs) are known to be toxic to many life forms, but little is known about their photooxidation products in the aqueous phase. We here identify a large number of photoproducts from 11 benzothiophenes, a polycyclic aromatic sulfur heterocycle that is a major representative of PACs in crude oil. The investigated compounds contain two to four methyl groups and an ethyl or an n-octyl group. In water, the products arise through oxidation of alkyl side chains to aldehydes and carboxylic acids or through an opening in one of the aromatic rings. The product analysis was performed using gas chromatography with mass spectrometric or atomic emission detection. The main product is always a sulfobenzoic acid, which strongly lowers the pH of the solution. With long alkyl substituents, surfactants are formed, which may possess solubilizing properties in water. The larger the number of alkyl groups, the faster is the photooxidation. Several of the identified acidic compounds were also found when whole crude oil was photooxidized, showing that simulation with individual compounds reflects the situation in whole crude.

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

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

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

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

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

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

Polycyclic aromatic hydrocarbons associated with road deposited solid and their ecological risk: Implications for road stormwater reuse.

PubMed

Liu, Liang; Liu, An; Li, Yang; Zhang, Lixun; Zhang, Guijuan; Guan, Yuntao

2016-09-01

Reusing stormwater is becoming popular worldwide. However, urban road stormwater commonly contains toxic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), which could undermine reuse safety. This study investigated pollution level of PAHs and their composition build-up on urban roads in a typical megacity in South China. The potential ecological risk posed by PAHs associated with road deposited solid (RDS) was also assessed. Results showed that ecological risk levels varied based on different land use types, which could be significantly influenced by the composition of PAHs and characteristics of RDS. A higher percentage of high-ring PAHs, such as more than four rings, could pose higher ecological risk and are more likely to undermine stormwater reuse safety. Additionally, the degree of traffic congestion rather than traffic volume was found to exert a more significant influence on the generation of high-ring PAH generation. Therefore, stormwater from more congested roads might need proper treatment (particularly for removing high-ring PAHs) before reuse or could be suitable for purposes requiring low-water-quality. The findings of this study are expected to contribute to adequate stormwater reuse strategy development and to enhance the safety of urban road stormwater reuse. Copyright © 2016 Elsevier B.V. All rights reserved.

Electron energy loss spectra of polycyclic aromatic hydrocarbons

NASA Technical Reports Server (NTRS)

Keller, John W.; Coplan, M. A.; Goruganthu, R.

1992-01-01

A survey of the electron energy-loss spectroscopy is reported of gas-phase polycyclic aromatic hydrocarbon (PAH) molecules consisting of up to seven rings where the study is limited to the more thermodynamically stable pericondensed systems. The aim of this work is to obtain absorption profiles (proportional to the oscillator strengths) from the visible to the soft X-ray region near 30 eV.

Polycyclic aromatic hydrocarbon (PAH) emissions from a coal-fired pilot FBC system.

PubMed

Liu, K; Han, W; Pan, W P; Riley, J T

2001-06-29

Due to the extensive amount of data suggesting the hazards of these compounds, 16 polycyclic aromatic hydrocarbons (PAHs) are on the Environmental Protection Agency (EPA) Priority Pollutant List. Emissions of these PAHs in the flue gas from the combustion of four coals were measured during four 1000h combustion runs using the 0.1MW heat-input (MWth) bench-scale fluidized bed combustor (FBC). An on-line sampling system was designed for the 16 PAHs, which consisted of a glass wool filter, condenser, glass fiber filter, Teflon filter, and a Tenax trap. The filters and Tenax were extracted by methylene chloride and hexane, respectively, followed by GC/MS analysis using the selective ion monitoring (SIM) mode. In this project, the effects of operating parameters, limestone addition, chlorine content in the coal, and Ca/S molar ratio on the emissions of PAHs were studied. The results indicated that the emissions of PAHs in an FBC system are primarily dependent on the combustion temperature and excess air ratio. The injection of secondary air with high velocity in the freeboard effectively reduces PAH emissions. The addition of extra limestone can promote the formation of PAHs in the FBC system. Chlorine in the coal can possibly lead to large benzene ring PAH formation during combustion. The total PAH emission increases with an increase in the sulfur content of coal. Incomplete combustion results in PAHs with four or more benzene rings. High efficiency combustion results in PAHs with two or three benzene rings.

Distributions of polycyclic aromatic hydrocarbons in surface waters, sediments and soils of Hangzhou City, China.

PubMed

Chen, Baoliang; Xuan, Xiaodong; Zhu, Lizhong; Wang, Jing; Gao, Yanzheng; Yang, Kun; Shen, Xueyou; Lou, Baofeng

2004-09-01

Ten polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in 17 surface water samples and 11 sediments of four water bodies, and 3 soils near the water-body bank in Hangzhou, China in December 2002. It was observed that the sum of PAHs concentrations ranged from 0.989 to 9.663 microg/L in surface waters, from 132.7 to 7343 ng/g dry weight in sediments, and from 59.71 to 615.8 ng/g dry weight in soils. The composition pattern of PAHs by ring size in water, sediment and soil were surveyed. Three-ring PAHs were dominated in surface waters and soils, meanwhile sediments were mostly dominated by four-ring PAHs. Furthermore, PAHs apparent distribution coefficients (K(d)) and solid f(oc)-normalized K(d) (e.g. K(oc)= K(d) / f(oc)) were calculated. The relationship between logK(oc) and logK(ow) of PAHs for field data on sediments and predicted values were compared. The sources of PAHs in different water bodies were evaluated by comparison of K (oc) values in sediments of the river downstream with that in soils. Hangzhou section of the Great Canal was heavily polluted by PAHs released from industrial wastewater in the past and now PAHs in sediment may serve as sources of PAHs in surface water. PAHs in Qiantang River were contributed from soil runoff. Municipal road runoff was mostly contributed to West Lake PAHs.

Role of Kekulé and Non-Kekulé Structures in the Radical Character of Alternant Polycyclic Aromatic Hydrocarbons: A TAO-DFT Study

PubMed Central

Yeh, Chia-Nan; Chai, Jeng-Da

2016-01-01

We investigate the role of Kekulé and non-Kekulé structures in the radical character of alternant polycyclic aromatic hydrocarbons (PAHs) using thermally-assisted-occupation density functional theory (TAO-DFT), an efficient electronic structure method for the study of large ground-state systems with strong static correlation effects. Our results reveal that the studies of Kekulé and non-Kekulé structures qualitatively describe the radical character of alternant PAHs, which could be useful when electronic structure calculations are infeasible due to the expensive computational cost. In addition, our results support previous findings on the increase in radical character with increasing system size. For alternant PAHs with the same number of aromatic rings, the geometrical arrangements of aromatic rings are responsible for their radical character. PMID:27457289

Bioaccumulation of polycyclic aromatic hydrocarbons and survival of earthworms (Eisenia andrei) exposed to biochar amended soils.

PubMed

Malev, O; Contin, M; Licen, S; Barbieri, P; De Nobili, M

2016-02-01

Biochar has a charcoal polycyclic aromatic structure which allows its long half-life in soil, making it an ideal tool for C sequestration and for adsorption of organic pollutants, but at the same time raises concerns about possible adverse impacts on soil biota. Two biochars were tested under laboratory-controlled conditions on Eisenia andrei earthworms: a biochar produced at low temperature from wine tree cuttings (WTB) and a commercial low tar hardwood lump charcoal (HLB). The avoidance test (48-h exposure) showed that earthworms avoid biochar-treated soil with rates higher than 16 t ha(-1) for HLB and 64 t ha(-1) for WTB. After 42 days, toxic effects on earthworms were observed even at application rates (100 t ha(-1)) that are generally considered beneficial for most crops. The concentration of HLB and WTB required to kill half of earthworms' population (LC50; 95% confidence limits) in the synthetic OECD soil was 338 and 580 t ha(-1), respectively. Accumulation of polycyclic aromatic hydrocarbons (PAH) in earthworms exposed to the two biochar types at 100 t ha(-1) was tested in two soils of different texture. In biochar-treated soils, the average earthworm survival rates were about 64% in the sandy and 78% clay-loam soils. PAH accumulation was larger in the sandy soil and largest in soils amended with HLB. PAH with less than four rings were preferentially scavenged from the soil by biochars, and this behaviour may mask that of the more dangerous components (i.e. four to five rings), which are preferentially accumulated. Earthworms can accumulate PAH as a consequence of exposure to biochar-treated soils and transfer them along the food chain. Soil type and biochar quality are both relevant in determining PAH transfer.

Comparing Urinary Biomarkers of Airborne and Dermal Exposure to Polycyclic Aromatic Compounds in Asphalt-Exposed Workers

PubMed Central

Sobus, Jon R.; McClean, Michael D.; Herrick, Robert F.; Waidyanatha, Suramya; Nylander-French, Leena A.; Kupper, Lawrence L.; Rappaport, Stephen M.

2009-01-01

When working with hot mix asphalt, road pavers are exposed to polycyclic aromatic hydrocarbons (PAHs) through the inhalation of vapors and particulate matter (PM) and through dermal contact with PM and contaminated surfaces. Several PAHs with four to six rings are potent carcinogens which reside in these particulate emissions. Since urinary biomarkers of large PAHs are rarely detectable in asphalt workers, attention has focused upon urinary levels of the more volatile and abundant two-ring and three-ring PAHs as potential biomarkers of PAH exposure. Here, we compare levels of particulate polycyclic aromatic compounds (P-PACs, a group of aromatic hydrocarbons containing PAHs and heterocyclic compounds with four or more rings) in air and dermal patch samples from 20 road pavers to the corresponding urinary levels of naphthalene (U-Nap) (two rings), phenanthrene (U-Phe) (three rings), monohydroxylated metabolites of naphthalene (OH-Nap) and phenanthrene (OH-Phe), and 1-hydroxypyrene (OH-Pyr) (four rings), the most widely used biomarker of PAH exposure. For each worker, daily breathing-zone air (n = 55) and dermal patch samples (n = 56) were collected on three consecutive workdays along with postshift, bedtime, and morning urine samples (n = 149). Measured levels of P-PACs and the urinary analytes were used to statistically model exposure–biomarker relationships while controlling for urinary creatinine, smoking status, age, body mass index, and the timing of urine sampling. Levels of OH-Phe in urine collected postshift, at bedtime, and the following morning were all significantly associated with levels of P-PACs in air and dermal patch samples. For U-Nap, U-Phe, and OH-Pyr, both air and dermal patch measurements of P-PACs were significant predictors of postshift urine levels, and dermal patch measurements were significant predictors of bedtime urine levels (all three analytes) and morning urine levels (U-Nap and OH-Pyr only). Significant effects of creatinine concentration were observed for all analytes, and modest effects of smoking status and body mass index were observed for U-Phe and OH-Pyr, respectively. Levels of OH-Nap were not associated with P-PAC measurements in air or dermal patch samples but were significantly affected by smoking status, age, day of sample collection, and urinary creatinine. We conclude that U-Nap, U-Phe, OH-Phe, and OH-Pyr can be used as biomarkers of exposure to particulate asphalt emissions, with OH-Phe being the most promising candidate. Indications that levels of U-Nap, U-Phe, and OH-Pyr were significantly associated with dermal patch measurements well into the evening after a given work shift, combined with the small ratios of within-person variance components to between-person variance components at bedtime, suggest that bedtime measurements may be useful for investigating dermal PAH exposures. PMID:19602502

Birds and polycyclic aromatic hydrocarbons

USGS Publications Warehouse

Albers, P.H.

2006-01-01

Polycyclic aromatic hydrocarbons (PAH) are present throughout the global environment and are produced naturally and by activities of humans. Effects of PAH on birds have been determined by studies employing egg injection, egg immersion, egg shell application, single and multiple oral doses, subcutaneous injection, and chemical analysis of field-collected eggs and tissue. The four-to six-ring aromatic compounds are the most toxic to embryos, young birds, and adult birds. For embryos, effects include death, developmental abnormalities, and a variety of cellular and biochemical responses. For adult and young birds, effects include reduced egg production and hatching, increased clutch or brood abandonment, reduced growth, increased organweights, and a variety of biochemical responses. Trophic level accumulation is unlikely. Environmental exposure to PAH in areas of high human population or habitats affected by recent petroleum spills might be sufficient to adversely affect reproduction. Evidence of long-term effects of elevated concentrations of environmental PAH on bird populations is very limited and the mechanisms of effect are unclear.

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

Biotransformation of the high-molecular weight polycyclic aromatic hydrocarbon (PAH) benzo[k]fluoranthene by Sphingobium sp. strain KK22 and identification of new products of non-alternant PAH biodegradation by liquid chromatography electrospray ionization tandem mass spectrometry

PubMed Central

Maeda, Allyn H; Nishi, Shinro; Hatada, Yuji; Ozeki, Yasuhiro; Kanaly, Robert A

2014-01-01

A pathway for the biotransformation of the environmental pollutant and high-molecular weight polycyclic aromatic hydrocarbon (PAH) benzo[k]fluoranthene by a soil bacterium was constructed through analyses of results from liquid chromatography negative electrospray ionization tandem mass spectrometry (LC/ESI(–)-MS/MS). Exposure of Sphingobium sp. strain KK22 to benzo[k]fluoranthene resulted in transformation to four-, three-and two-aromatic ring products. The structurally similar four-and three-ring non-alternant PAHs fluoranthene and acenaphthylene were also biotransformed by strain KK22, and LC/ESI(–)-MS/MS analyses of these products confirmed the lower biotransformation pathway proposed for benzo[k]fluoranthene. In all, seven products from benzo[k]fluoranthene and seven products from fluoranthene were revealed and included previously unreported products from both PAHs. Benzo[k]fluoranthene biotransformation proceeded through ortho-cleavage of 8,9-dihydroxy-benzo[k]fluoranthene to 8-carboxyfluoranthenyl-9-propenic acid and 9-hydroxy-fluoranthene-8-carboxylic acid, and was followed by meta-cleavage to produce 3-(2-formylacenaphthylen-1-yl)-2-hydroxy-prop-2-enoic acid. The fluoranthene pathway converged with the benzo[k]fluoranthene pathway through detection of the three-ring product, 2-formylacenaphthylene-1-carboxylic acid. Production of key downstream metabolites, 1,8-naphthalic anhydride and 1-naphthoic acid from benzo[k]fluoranthene, fluoranthene and acenaphthylene biotransformations provided evidence for a common pathway by strain KK22 for all three PAHs through acenaphthoquinone. Quantitative analysis of benzo[k]fluoranthene biotransformation by strain KK22 confirmed biodegradation. This is the first pathway proposed for the biotransformation of benzo[k]fluoranthene by a bacterium. PMID:24325265

Thermodynamic and kinetic characterization of polycyclic aromatic hydrocarbons in reversed-phase liquid chromatography.

PubMed

Howerton, Samuel B; McGuffin, Victoria L

2003-07-15

The retention of six polycyclic aromatic hydrocarbons (PAHs) was characterized by reversed-phase liquid chromatography. The PAHs were detected by laser-induced fluorescence at four points along an optically transparent capillary column. The profiles were characterized in space and time using an exponentially modified Gaussian equation. The resulting parameters were used to calculate the retention factors, as well as the concomitant changes in molar enthalpy and molar volume, for each PAH on monomeric (2.7 micromol/m2) and polymeric (5.4 micromol/m2) octadecylsilica. The changes in molar enthalpy become more exothermic as ring number increases and as annelation structure becomes less condensed. The changes in molar volume become more negative as ring number increases for the planar PAHs, but are positive for the nonplanar solutes. In addition, the rate constants, as well as the concomitant activation enthalpy and activation volume, are calculated for the first time. The kinetic data demonstrate that many of the PAHs exhibit very fast transitions between the mobile and stationary phases. The transition state is very high in energy, and the activation enthalpies and volumes become greater as ring number increases and as annelation structure becomes less condensed. The changes in thermodynamic and kinetic behavior are much more pronounced for the polymeric phase than for the monomeric phase.

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.

[Effects of smoking on the concentrations of urinary 10 metabolites of polycyclic aromatic hydrocarbons in coke oven workers].

PubMed

He, Yun-feng; Zhang, Wang-zhen; Kuang, Dan; Deng, Hua-xin; Li, Xiao-hai; Lin, Da-feng; Deng, Qi-fei; Huang, Kun; Wu, Tang-chun

2012-12-01

To explore the effects of smoking on urinary 10 metabolites of polycyclic aromatic hydrocarbons (PAHs) in the coke oven workers. Occupational health examination was performed on 1401 coke oven workers in one coking plant, their urine were collected respectively. The concentrations of the ten monohydroxy polycyclic aromatic hydrocarbons in urine were detected by gas chromatography/mass spectrometry. The 1401 workers were divided into four groups, namely control, adjunct workplaces, bottom and side, top group according to their workplaces and the different concentrations of PAHs in the environment. The concentrations of the ten monohydroxy polycyclic aromatic hydrocarbons between smokers and nonsmokers in each workplace group were compared using analysis of covariance, respectively. The levels of concentrations of the sixteen polycyclic aromatic hydrocarbons we detected at control were significantly higher than those at other areas (P < 0.05). Comparing the ten monohydroxy polycyclic aromatic hydrocarbons levels between smokers and nonsmokers, the levels of 1-hydroxynaphthalene and 2-hydroxynaphthalene among smokers were higher than nonsmokers with statistically significance in control, adjunct workplaces, bottom and side and top groups (P < 0.05). However, the levels of 1-hydroxypyrene had no statistically significant differences between the four areas. Urinary 1-hydroxynaphthalene and 2-hydroxynaphthalene may be used as biomarkers for the impact of smoking on monohydroxy polycyclic aromatic hydrocarbons in the coke oven workers.

Quantum control of coherent π -electron ring currents in polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Mineo, Hirobumi; Fujimura, Yuichi

2017-12-01

We present results for quantum optimal control (QOC) of the coherent π electron ring currents in polycyclic aromatic hydrocarbons (PAHs). Since PAHs consist of a number of condensed benzene rings, in principle, there exist various coherent ring patterns. These include the ring current localized to a designated benzene ring, the perimeter ring current that flows along the edge of the PAH, and the middle ring current of PAHs having an odd number of benzene rings such as anthracene. In the present QOC treatment, the best target wavefunction for generation of the ring current through a designated path is determined by a Lagrange multiplier method. The target function is integrated into the ordinary QOC theory. To demonstrate the applicability of the QOC procedure, we took naphthalene and anthracene as the simplest examples of linear PAHs. The mechanisms of ring current generation were clarified by analyzing the temporal evolutions of the electronic excited states after coherent excitation by UV pulses or (UV+IR) pulses as well as those of electric fields of the optimal laser pulses. Time-dependent simulations of the perimeter ring current and middle ring current of anthracene, which are induced by analytical electric fields of UV pulsed lasers, were performed to reproduce the QOC results.

Airborne Exposures to Polycyclic Aromatic Compounds Among Workers in Asphalt Roofing Manufacturing Facilities.

PubMed

Trumbore, David C; Osborn, Linda V; Johnson, Kathleen A; Fayerweather, William E

2015-01-01

We studied exposure of 151 workers to polycyclic aromatic compounds and asphalt emissions during the manufacturing of asphalt roofing products-including 64 workers from 10 asphalt plants producing oxidized, straight-run, cutback, and wax- or polymer-modified asphalts, and 87 workers from 11 roofing plants producing asphalt shingles and granulated roll roofing. The facilities were located throughout the United States and used asphalt from many refiners and crude oils. This article helps fill a gap in exposure data for asphalt roofing manufacturing workers by using a fluorescence technique that targets biologically active 4-6 ring polycyclic aromatic compounds and is strongly correlated with carcinogenic activity in animal studies. Worker exposures to polycyclic aromatic compounds were compared between manufacturing plants, at different temperatures and using different raw materials, and to important external benchmarks. High levels of fine limestone particulate in the plant air during roofing manufacturing increased polycyclic aromatic compound exposure, resulting in the hypothesis that the particulate brought adsorbed polycyclic aromatic compounds to the worker breathing zone. Elevated asphalt temperatures increased exposures during the pouring of asphalt. Co-exposures in these workplaces which act as confounders for both the measurement of total organic matter and fluorescence were detected and their influence discussed. Exposures to polycyclic aromatic compounds in asphalt roofing manufacturing facilities were lower than or similar to those reported in hot-mix paving application studies, and much below those reported in studies of hot application of built-up roofing asphalt. These relatively low exposures in manufacturing are primarily attributed to air emission controls in the facilities, and the relatively moderate temperatures, compared to built-up roofing, used in these facilities for oxidized asphalt. The exposure to polycyclic aromatic compounds was a very small part of the overall worker exposure to asphalt fume, on average less than 0.07% of the benzene-soluble fraction. Measurements of benzene-soluble fraction were uniformly below the American Conference of Governmental Industrial Hygienists' Threshold Limit Value for asphalt fume.

Atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in Shanghai: the spatio-temporal variation and source identification

NASA Astrophysics Data System (ADS)

Cheng, Chen; Bi, Chunjuan; Wang, Dongqi; Yu, Zhongjie; Chen, Zhenlou

2018-03-01

This study investigated the dry and wet deposition fluxes of atmospheric polycyclic aromatic hydrocarbons (PAHs) in Shanghai, China. The flux sources were traced based on composition and spatio-temporal variation. The results show that wet deposition concentrations of PAHs ranged from 0.07 to 0.67 mg·L-1 and were correlated with temperature ( P<0.05). Dry deposition of PAHs concentrations ranged from 3.60-92.15 mg·L-1 and were higher in winter and spring than in summer and autumn. The annual PAH average fluxes were 0.631 mg·m-2·d-1 and 4.06 mg·m-2·d-1 for wet and dry deposition, respectively. The highest wet deposition of PAH fluxes was observed in summer, while dry deposition fluxes were higher in winter and spring. Atmospheric PAHs were deposited as dry deposition in spring and winter, yet wet deposition was the dominant pathway during summer. Total atmospheric PAH fluxes were higher in the northern areas than in the southern areas of Shanghai, and were also observed to be higher in winter and spring. Annual deposition of atmospheric PAHs was about 10.8 t in across all of Shanghai. Wet deposition of PAHs was primarily composed of two, three, or four rings, while dry deposition of PAHs was composed of four, five, or six rings. The atmospheric PAHs, composed of four, five, or six rings, primarily existed in the form of particulates. Coal combustion and vehicle emissions were the dominant sources of PAH in the observed area of downtown Shanghai. In suburban areas, industrial pollution, from sources such as coke oven, incinerator, and oil fired power plant, was as significant as vehicle emissions in contributing to the deposition of PAHs.

Application of a self-organizing map and positive matrix factorization to investigate the spatial distributions and sources of polycyclic aromatic hydrocarbons in soils from Xiangfen County, northern China.

PubMed

Tao, Shi-Yang; Zhong, Bu-Qing; Lin, Yan; Ma, Jin; Zhou, Yongzhang; Hou, Hong; Zhao, Long; Sun, Zaijin; Qin, Xiaopeng; Shi, Huading

2017-07-01

The concentrations of 16 priority polycyclic aromatic hydrocarbons (PAHs) were measured in 128 surface soil samples from Xiangfen County, northern China. The total mass concentration of these PAHs ranged from 52 to 10,524ng/g, with a mean of 723ng/g. Four-ring PAHs contributed almost 50% of the total PAH burden. A self-organizing map and positive matrix factorization were applied to investigate the spatial distribution and source apportionment of PAHs. Three emission sources of PAHs were identified, namely, coking ovens (21.9%), coal/biomass combustion (60.1%), and anthracene oil (18.0%). High concentrations of low-molecular-weight PAHs were particularly apparent in the coking plant zone in the region around Gucheng Town. High-molecular-weight PAHs mainly originated from coal/biomass combustion around Gucheng Town, Xincheng Town, and Taosi Town. PAHs in the soil of Xiangfen County are unlikely to pose a significant cancer risk for the population. Copyright © 2017 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.

Source apportionment of atmospheric polycyclic aromatic hydrocarbons (PAHs) in Palm Beach County, Florida.

PubMed

Afshar-Mohajer, Nima; Wilson, Christina; Wu, Chang-Yu; Stormer, James E

2016-04-01

Due to concerns about adverse health effects associated with inhalation of atmospheric polycyclic aromatic hydrocarbons (PAHs), 30 ambient air samples were obtained at an air quality monitoring station in Palm Beach County, Florida, from March 2013 to March 2014. The ambient PAH concentration measurements and fractional emission rates of known sources were incorporated into a chemical mass balance model, CMB8.2, developed by EPA, to apportion contributions of three major PAH sources including preharvest sugarcane burning, mobile vehicles, and wildland fires. Strong association between the number of benzene rings and source contribution was found, and mobile vehicles were identified to be the prevailing source (contribution≥56%) for the observed PAHs concentration with lower molecular weights (four or fewer benzene rings) throughout the year. Preharvest sugarcane burning was the primary contributing source for PAHs with relatively higher molecular weights (five or more benzene rings) during the sugarcane burning season (from October to May of the next year). Source contribution of wildland fires varied among PAH compounds but was consistently lower than for sugarcane burning during the sugarcane harvest season. Determining the major sources responsible for ground-level PAHs serves as a tool to improving management strategies for PAH emitting sources and a step toward better protection of the health of residents in terms of exposure to PAHs. The results obtain insight into temporal dominance of PAH polluting sources for those residential areas located near sugarcane burning facilities and have implications beyond Palm Beach County, in areas with high concerns of PAHs and their linked sources. Source apportionment of atmospheric polycyclic hydrocarbons (PAHs) in Palm Beach County, Florida, meant to estimate contributions of major sources in PAH concentrations measured at Belle Glade City of Palm Beach County. Number of benzene rings was found to be the key parameter in determining the source with the prevailing contribution. Mobile vehicle sources showed a higher contribution for species with four or fewer benzene rings, whereas sugarcane burning contributed more for species with five or more benzene rings. Results from this study encourage more control for sugarcane burns and help to better manage authorization of the sugarcane burning incidents and more restrictive transportation plans to limit PAH emissions from mobile vehicles.

Biotransformation of the high-molecular weight polycyclic aromatic hydrocarbon (PAH) benzo[k]fluoranthene by Sphingobium sp. strain KK22 and identification of new products of non-alternant PAH biodegradation by liquid chromatography electrospray ionization tandem mass spectrometry.

PubMed

Maeda, Allyn H; Nishi, Shinro; Hatada, Yuji; Ozeki, Yasuhiro; Kanaly, Robert A

2014-03-01

A pathway for the biotransformation of the environmental pollutant and high-molecular weight polycyclic aromatic hydrocarbon (PAH) benzo[k]fluoranthene by a soil bacterium was constructed through analyses of results from liquid chromatography negative electrospray ionization tandem mass spectrometry (LC/ESI(-)-MS/MS). Exposure of Sphingobium sp. strain KK22 to benzo[k]fluoranthene resulted in transformation to four-, three- and two-aromatic ring products. The structurally similar four- and three-ring non-alternant PAHs fluoranthene and acenaphthylene were also biotransformed by strain KK22, and LC/ESI(-)-MS/MS analyses of these products confirmed the lower biotransformation pathway proposed for benzo[k]fluoranthene. In all, seven products from benzo[k]fluoranthene and seven products from fluoranthene were revealed and included previously unreported products from both PAHs. Benzo[k]fluoranthene biotransformation proceeded through ortho-cleavage of 8,9-dihydroxy-benzo[k]fluoranthene to 8-carboxyfluoranthenyl-9-propenic acid and 9-hydroxy-fluoranthene-8-carboxylic acid, and was followed by meta-cleavage to produce 3-(2-formylacenaphthylen-1-yl)-2-hydroxy-prop-2-enoic acid. The fluoranthene pathway converged with the benzo[k]fluoranthene pathway through detection of the three-ring product, 2-formylacenaphthylene-1-carboxylic acid. Production of key downstream metabolites, 1,8-naphthalic anhydride and 1-naphthoic acid from benzo[k]fluoranthene, fluoranthene and acenaphthylene biotransformations provided evidence for a common pathway by strain KK22 for all three PAHs through acenaphthoquinone. Quantitative analysis of benzo[k]fluoranthene biotransformation by strain KK22 confirmed biodegradation. This is the first pathway proposed for the biotransformation of benzo[k]fluoranthene by a bacterium. © 2013 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Actions of a versatile fluorene-degrading bacterial isolate on polycyclic aromatic compounds.

PubMed Central

Grifoll, M; Selifonov, S A; Gatlin, C V; Chapman, P J

1995-01-01

Pseudomonas cepacia F297 grew with fluorene as a sole source of carbon and energy; its growth yield corresponded to an assimilation of about 40% of fluorene carbon. The accumulation of a ring meta-cleavage product during growth and the identification of 1-indanone in growth media and washed-cell suspensions suggest that strain F297 metabolizes fluorene by mechanisms analogous to those of naphthalene degradation. In addition to fluorene, strain F297 utilized for growth a wide variety of polycyclic aromatic compounds (PACs), including naphthalene, 2,3-dimethylnaphthalene, phenanthrene, anthracene, and dibenzothiophene. Fluorene-induced cells of the strain also transformed 2,6-dimethylnaphthalene, biphenyl, dibenzofuran, acenaphthene, and acenaphthylene. The identification of products formed from those substrates (by gas chromatography-mass spectrometry) in washed-cell suspensions indicates that P. cepacia F297 carries out the following reactions: (i) aromatic ring oxidation and cleavage, apparently using the pyruvate released for growth, (ii) methyl group oxidations, (iii) methylenic oxidations, and (iv) S oxidations of aromatic sulfur heterocycles. Strain F297 grew with a creosote-PAC mixture, producing an almost complete removal of all aromatic compounds containing 2 to 3 rings in 14 days, as demonstrated by gas chromatography analysis of the remaining PACs recovered from cultures. The identification of key chemicals confirmed that not only are certain compounds depleted but also the anticipated reaction products are found. PMID:7487007

Actions of a versatile fluorene-degrading bacterial isolate on polycyclic aromatic compounds.

PubMed

Grifoll, M; Selifonov, S A; Gatlin, C V; Chapman, P J

1995-10-01

Pseudomonas cepacia F297 grew with fluorene as a sole source of carbon and energy; its growth yield corresponded to an assimilation of about 40% of fluorene carbon. The accumulation of a ring meta-cleavage product during growth and the identification of 1-indanone in growth media and washed-cell suspensions suggest that strain F297 metabolizes fluorene by mechanisms analogous to those of naphthalene degradation. In addition to fluorene, strain F297 utilized for growth a wide variety of polycyclic aromatic compounds (PACs), including naphthalene, 2,3-dimethylnaphthalene, phenanthrene, anthracene, and dibenzothiophene. Fluorene-induced cells of the strain also transformed 2,6-dimethylnaphthalene, biphenyl, dibenzofuran, acenaphthene, and acenaphthylene. The identification of products formed from those substrates (by gas chromatography-mass spectrometry) in washed-cell suspensions indicates that P. cepacia F297 carries out the following reactions: (i) aromatic ring oxidation and cleavage, apparently using the pyruvate released for growth, (ii) methyl group oxidations, (iii) methylenic oxidations, and (iv) S oxidations of aromatic sulfur heterocycles. Strain F297 grew with a creosote-PAC mixture, producing an almost complete removal of all aromatic compounds containing 2 to 3 rings in 14 days, as demonstrated by gas chromatography analysis of the remaining PACs recovered from cultures. The identification of key chemicals confirmed that not only are certain compounds depleted but also the anticipated reaction products are found.

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

PHOTOACTIVATION AND TOXICITY OF MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBON COMPOUNDS IN MARINE SEDIMENT

EPA Science Inventory

The direct toxicity and photoinduced toxicity of sediment-associated acenaphthene, phenanthrene, fluoranthene, and pyrene were determined for the marine amphipod Rhepoxynius abronius. The four polycyclic aromatic hydrocarbons (PAHs) were spiked into sediment in a concentration se...

Prediction of the Ultraviolet-Visible Absorption Spectra of Polycyclic Aromatic Hydrocarbons (Dibenzo and Naphtho) Derivatives of Fluoranthene.

PubMed

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

2017-06-01

The annellation theory method has been used to predict the locations of maximum absorbance (LMA) of the ultraviolet-visible (UV-Vis) spectral bands in the group of polycyclic aromatic hydrocarbons (PAHs) C 24 H 14 (dibenzo and naphtho) derivatives of fluoranthene (DBNFl). In this group of 21 PAHs, ten PAHs present a sextet migration pattern with four or more benzenoid rings that is potentially related to a high molecular reactivity and high mutagenic conduct. This is the first time that the locations of maximum absorbance in the UV-Vis spectra of naphth[1,2- a]aceanthrylene, dibenz[ a,l]aceanthrylene, indeno[1,2,3- de]naphthacene, naphtho[1,2- j]fluoranthene, naphth[2,1- e]acephenanthrylene, naphth[2,1- a]aceanthrylene, dibenz[ a,j]aceanthrylene, naphth[1,2- e]acephenanthrylene, and naphtho[2,1- j]fluoranthene have been predicted. Also, this represents the first report about the application of the annellation theory for the calculation of the locations of maximum absorbance in the UV-Vis spectra of PAHs with five-membered rings. Furthermore, this study constitutes the premier investigation beyond the pure benzenoid classical approach toward the establishment of a generalized annellation theory that will encompass not only homocyclic benzenoid and non-benzenoid PAHs, but also heterocyclic compounds.

Catchment scale assessment of risk posed by traffic generated heavy metals and polycyclic aromatic hydrocarbons.

PubMed

Ma, Yukun; McGree, James; Liu, An; Deilami, Kaveh; Egodawatta, Prasanna; Goonetilleke, Ashantha

2017-10-01

Heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) are among the most toxic chemical pollutants present in urban stormwater. Consequently, urban stormwater reuse is constrained due to the human health risk posed by these pollutants. This study developed a scientifically robust approach to assess the risk to human health posed by HMs and PAHs in urban stormwater in order to enhance its reuse. Accordingly, an innovative methodology was created consisting of four stages: quantification of traffic and land use parameters; estimation of pollutant concentrations for model development; risk assessment, and risk map presentation. This methodology will contribute to catchment scale assessment of the risk associated with urban stormwater and for risk mitigation. The risk map developed provides a simple and efficient approach to identify the critical areas within a large catchment. The study also found that heavy molecular weight PAHs (PAHs with 5-6 benzene rings) in urban stormwater pose higher risk to human health compared to light molecular PAHs (PAHs with 2-4 benzene rings). These outcomes will facilitate the development of practical approaches for applying appropriate mitigation measures for the safe management of urban stormwater pollution and for the identification of enhanced reuse opportunities. Copyright © 2017 Elsevier Inc. All rights reserved.

Reflectance spectroscopy (350-2500 nm) of solid-state polycyclic aromatic hydrocarbons (PAHs)

NASA Astrophysics Data System (ADS)

Izawa, M. R. M.; Applin, D. M.; Norman, L.; Cloutis, E. A.

2014-07-01

Polycyclic aromatic hydrocarbons (PAHs) are organic compounds based on fused aromatic rings, and are formed in a variety of astrophysical, solar nebula and planetary processes. Polycyclic aromatic hydrocarbons are known or suspected to occur in a wide variety of planetary settings including icy satellites, Titan’s hazes, carbonaceous meteorites, comet nuclei, ring particles; and terrestrial organic-rich lithologies such as coals, asphaltites, and bituminous sands. Relatively few measurements of the visible and near-infrared spectra of PAHs exist, yet this wavelength region (350-2500 nm) is widely used for remote sensing. This study presents detailed analyses of the 350-2500 nm reflectance spectra of 47 fine-grained powders of different high-purity solid-state PAHs. Spectral properties of PAHs change with variations in the number and connectivity of linked aromatic rings and the presence and type of side-groups and heterocycles. PAH spectra are characterized by three strong features near ∼880 nm, ∼1145 nm, and ∼1687 nm due to overtones of νCH fundamental stretching vibrations. Some PAHs are amenable to remote detection due to the presence of diagnostic spectral features, including: Nsbnd H stretching overtones at 1490-1515 nm in NH- and NH2-bearing PAHs, aliphatic or saturated bond Csbnd H overtone vibrations at ∼1180-1280 nm and ∼1700-1860 nm; a broad asymmetric feature between ∼1450 nm and ∼1900 nm due to Osbnd H stretching overtones in aromatic alcohols, Csbnd H and Cdbnd O combinations near ∼2000-2010 nm and ∼2060-2270 nm in acetyl and carboxyl-bearing PAHs. Other substituents such as sulphonyl, thioether ether and carboxyl heterocycles, or cyano, nitrate, and aromatic side groups, do not produce well-resolved diagnostic spectral features but do cause shifts in the positions of the aromatic Csbnd H vibrational overtone features. Fluorescence is commonly suppressed by the presence of heterocycles, side-groups and in many non-alternant PAHs. The spectral characteristics of PAHs offer the potential, under suitable circumstances, for remote characterization of the classes of PAH present and in some cases, identification of particular heterocyclic or side-group substituents.

Distribution, source analysis, and ecological risk assessment of polycyclic aromatic hydrocarbons in the typical topsoil of the Issyk-Kul Lake Basin.

PubMed

Liu, Wen; Ma, Long; Abuduwaili, Jilili; Li, Yaoming

2017-08-01

The concentration, distribution, compositional characteristics, and pollution sources of 16 polycyclic aromatic hydrocarbons (PAHs) in the topsoil of Issyk-Kul Lake Basin were studied, and their ecological risks were evaluated in this paper. The total concentration of the 16 PAHs was 68.58-475.95 ng g -1 , with an average of 134.45 ng g -1 . Four-ring PAHs accounted for 43.2% of the total PAHs, two- and three-ring PAHs accounted for 39.4%, and five- and six-ring PAHs accounted for 15.8%. The total concentration of the seven carcinogenic PAHs was 7.66-76.04 ng g -1 , with an average of 30.97 ng g -1 . An analysis of the PAH sources through diagnostic ratio analysis and principal component analysis was carried out. The results showed that the regional soil PAHs were mainly derived from coal, wood, and grass combustion, while traffic and regional industry also had small contributions to the PAHs. The pollution-free samples accounted for 75% and the slightly polluted samples accounted for 25% based on the total concentration of the 16 PAHs. An ecological risk assessment showed that 26.7% of Ac and 3.3% of Pyr and DahA might occasionally produce ecological risks. The toxicity was calculated on the basis of benzo[a]pyrene, and the toxicity equivalent was between 2.48 and 13.78 ng g -1 with an average of 6.23 ng g -1 , which currently does not pose any health risk to human life.

Formation of polycyclic aromatic hydrocarbons in circumstellar envelopes

NASA Technical Reports Server (NTRS)

Frenklach, Michael; Feigelson, Eric D.

1989-01-01

Production of polycyclic aromatic hydrocarbons in carbon-rich circumstellar envelopes was investigated using a kinetic approach. A detailed chemical reaction mechanism of gas-phase PAH formation and growth, containing approximately 100 reactions of 40 species, was numerically solved under the physical conditions expected in cool stellar winds. The chemistry is based on studies of soot production in hydrocarbon pyrolysis and combustion. Several first-ring and second-ring cyclization processes were considered. A linear lumping algorithm was used to describe PAH growth beyond the second aromatic ring. PAH production using this mechanism was examined with respect to a grid of idealized constant velocity stellar winds as well as several published astrophysical models. The basic result is that the onset of PAH production in the interstellar envelopes is predicted to occur within the temperature interval of 1100 to 900 K. The absolute amounts of the PAHs formed, however, are very sensitive to a number of parameters, both chemical and astrophysical, whose values are not accurately known. Astrophysically meaningful quantities of PAHs require particularly dense and slow stellar winds and high initial acetylene abundance. It is suggested that most of the PAHs may be produced in a relatively small fraction of carbon-rich red giants.

Virtual Exploration of the Ring Systems Chemical Universe.

PubMed

Visini, Ricardo; Arús-Pous, Josep; Awale, Mahendra; Reymond, Jean-Louis

2017-11-27

Here, we explore the chemical space of all virtually possible organic molecules focusing on ring systems, which represent the cyclic cores of organic molecules obtained by removing all acyclic bonds and converting all remaining atoms to carbon. This approach circumvents the combinatorial explosion encountered when enumerating the molecules themselves. We report the chemical universe database GDB4c containing 916 130 ring systems up to four saturated or aromatic rings and maximum ring size of 14 atoms and GDB4c3D containing the corresponding 6 555 929 stereoisomers. Almost all (98.6%) of these ring systems are unknown and represent chiral 3D-shaped macrocycles containing small rings and quaternary centers reminiscent of polycyclic natural products. We envision that GDB4c can serve to select new ring systems from which to design analogs of such natural products. The database is available for download at www.gdb.unibe.ch together with interactive visualization and search tools as a resource for molecular design.

PERSONAL EXPOSURES TO POLYCYCLIC AROMATIC HYDROCARBONS ASSOCIATED WITH THE NHEXAS PILOT

EPA Science Inventory

Personal exposure monitoring for select polycyclic aromatic hydrocarbons (PAHs) was performed as part of the National Human Exposure Assessment Survey (NHEXAS) Pilot Study in Baltimore, MD. Twenty-four hour PM10 sample collections (~5.7 m3) were performed using personal envi...

Separation and characterization of polycyclic aromatic hydrocarbons and alkylphenols in coal derived solvents

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

Hurtubise, R.J.; Allen, T.W.; Hussain, A.

1981-03-29

Dry-column chromatography with an aluminum oxide stationary phase and a n-hexane-ether (19:1) mobile phase was used to separate polycyclic aromatic hydrocarbons (PAH) by ring size. Prior to the dry-column chromatography step, the coal derived solvents were added to an acid treated silica gel column and eluted with chloroform. This step removed pyridine-type nitrogen heterocycles. After separation of the individual ring fractions, the fractions were further separated by either thin layer chromatography (TLC) or high performance liquid chromatography (HPLC). If TLC was used, then after separation fluorescence profiles of each PAH ring fraction distributed on 30%-acetylated cellulose chromatoplates were obtained withmore » a spectrodensitometer. Measurement of fluorescence peak heights gave an approximate measure of the amount of the 3-, 4-, 5-, and 6- ring PAH. For HPLC separation, the 3- and 4- ring PAH fractions obtained from the dry-column chromatography step were separated with a ..mu..-Bondapak C/sub 18/ column and methanol:water (65:35) mobile phase. The HPLC separated PAH were characterized by chromatographic correlation factors and corrected fluorescence excitation spectra. Alkylphenols were identified in coal recycle solvent sample following separation by HPLC.« less

Effect of ZSM-5 acidity on aromatic product selectivity during upgrading of pine pyrolysis vapors

DOE PAGES

Engtrakul, Chaiwat; Mukarakate, Calvin; Starace, Anne K.; ...

2015-11-14

The impact of catalyst acidity on the selectivity of upgraded biomass pyrolysis products was studied by passing pine pyrolysis vapors over five ZSM-5 catalysts of varying acidity at 500 degrees C. The SiO 2-to-Al 2O 3 ratio (SAR) of the ZSM-5 zeolite was varied from 23 to 280 to control the acidity of the catalyst and the composition of upgraded products. The upgraded product stream was analyzed by GCMS. Additionally, catalysts were characterized using temperature programmed desorption, diffuse-reflectance FTIR spectroscopy, N 2 physisorption, and X-ray diffraction. The results showed that the biomass pyrolysis vapors were highly deoxygenated to form amore » slate of aromatic hydrocarbons over all of the tested ZSM-5 catalysts. As the overall acidity of the ZSM-5 increased the selectivity toward alkylated (substituted) aromatics (e.g., xylene, dimethyl-naphthalene, and methyl-anthracene) decreased while the selectivity toward unsubstituted aromatics (e.g., benzene, naphthalene, and anthracene) increased. Additionally, the selectivity toward polycyclic aromatic compounds (2-ring and 3-ring) increased as catalyst acidity increased, corresponding to a decrease in acid site spacing. The increased selectivity toward less substituted polycyclic aromatic compounds with increasing acidity is related to the relative rates of cyclization and alkylation reactions within the zeolite structure. As the acid site concentration increases and sites become closer to each other, the formation of additional cyclization products occurs at a greater rate than alkylated products. The ability to adjust product selectivity within 1-, 2-, and 3-ring aromatic families, as well as the degree of substitution, by varying ZSM-5 acidity could have significant benefits in terms creating a slate of upgraded biomass pyrolysis products to meet specific target market demands.« less

A Naphtho- p-quinodimethane Exhibiting Baird’s (Anti)Aromaticity, Broken Symmetry, and Attractive Photoluminescence

DOE PAGES

Shokri, Siamak; Li, Jingbai; Manna, Manoj K.; ...

2017-08-24

In this paper, we report a novel reductive desulfurization reaction involving π-acidic naphthalene diimides 1 (NDI) using thionating agents such as Lawesson’s reagent. Along with the expected thionated NDI derivatives 2-6, new heterocyclic naphtho-p-quinodimethane compounds 7 depicting broken/reduced symmetry were successfully isolated and fully characterized. Empirical studies and theoretical modeling suggest that was formed via a six-membered ring oxathiaphosphenine intermediate rather than the usual four-membered ring oxathiaphosphetane of 2-6. Aside from the reduced symmetry in 7 as confirmed by single-crystal XRD analysis, we established that the ground state UV-vis absorption of 7 is red-shifted in comparison to the parent NDImore » 1. This result was expected in the case of thionated polycyclic diimides. However, unusual low energy transitions originate from Baird 4nπ aromaticity of compounds 7 in lieu of the intrinsic Huckel (4n + 2)π aromaticity as encountered in NDI 1. Moreover, complementary theoretical modeling results also corroborate this change in aromaticity of 7. Consequently, photophysical investigations show that, compared to parent NDI 1, 7 can easily access and emit from its T 1 state with a phosphorescence 3(7a)* lifetime of τ P = 395 μs at 77 K indicative of the formation of the corresponding “aromatic triplet” species according to the Baird’s rule of aromaticity.« less

Fungal lactone ring opening of 6', 7'-dihydroxybergamottin diminishes cytochrome P450 3A4 inhibitory activity

USDA-ARS?s Scientific Manuscript database

Furanocoumarins (FCs) are a class of aromatic compounds in grapefruit that inhibit human intestinal cytochrome P450 3A4 (CYP3A4). Since fungi metabolize polycyclic aromatic hydrocarbons, we hypothesized that certain fungi might also metabolize FCs into forms that may be inactive as CYP3A4 inhibitors...

INFLUENCE OF SOOT CARBON ON THE BIOACCULUMATION OF SEDIMENT-BOUND POLYCYCLIC AROMATIC HYDROCARBONS BY MARINE BENTHIC INVERTEBRATES: AN INTERSPECIES COMPARISON

EPA Science Inventory

The sorption of polycyclic aromatic hydrocarbons (PAHs) to soot carbon in marine sediments has been hypothesized to reduce PAH bioavailability. This hypothesis was tested for eight species of marine benthic invertebrates (four polychaete worms, Clymenella torquata, Nereis virens,...

Aromatic C=C bonds as dipolarophiles: facile reactions of uncomplexed electron-deficient benzene derivatives and other aromatic rings with a non-stabilized azomethine ylide.

PubMed

Lee, Sunyoung; Diab, Sonia; Queval, Pierre; Sebban, Muriel; Chataigner, Isabelle; Piettre, Serge R

2013-05-27

Non-stabilized azomethine ylide 4a reacts smoothly at room temperature with a variety of uncomplexed aromatic heterocycles and carbocycles on the condition that the ring contains at least one or two electron-withdrawing substituents, respectively. Aromatic substrates, including pyridine and benzene derivatives, participate as 2π components in [3+2] cycloaddition reactions and interact with one, two, or three equivalent(s) of the ylide, depending on their structure and substitution pattern. Thus, this process affords highly functionalized polycyclic structures that contain between one and three pyrrolidinyl ring(s) in useful yields. These results indicate that the site selectivity of the cycloaddition reactions strongly depends on both the nature and the positions of the substituents. In most cases, the second 1,3-dipolar reaction occurs on the opposite face to the one that contains the first pyrrolidinyl ring. DFT calculations on model compounds indicate that a concerted mechanism features a low activation barrier. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Petroleum hydrocarbons in the surface water of two estuaries in the Southeastern united states

NASA Astrophysics Data System (ADS)

Bidleman, T. F.; Castleberry, A. A.; Foreman, W. T.; Zaranski, M. T.; Wall, D. W.

1990-01-01

Surface water samples from Charleston Harbor, SC and Winyah Bay, SC were analysed for total hydrocarbons by gas chromatography (GC) and for petroleum residues (expressed as crude oil equivalents) by fluorescence spectrometry. Cleanup by column chromatography and saponification was necessary to reduce the background from extraneous fluorescing materials. Oil concentrations determined by FS ranged from 0·5-25 μg l -1 in Charleston Harbor and <0·23-9·6 μg l -1 in Winyah Bay. Hydrocarbons determined by GC were significantly correlated ( P < 0·01) with crude oil equivalents determined by FS, but the data showed considerable scatter as indicated by r2 = 0·45. Polycyclic aromatic hydrocarbons were determined by gas chromatography—mass spectrometry for one set of Winyah Bay samples. The sum of nonalkylated polycyclic aromatic hydrocarbons having ≥ 3 rings ranged from 7-64 ng l -1 at different stations. Perylene, possibly originating from sediment dredging, was one of the more abundant polycyclic aromatic hydrocarbons.

Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

2015-12-01

Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polycyclic Aromatic Hydrocarbons Adsorption onto Graphene: A DFT and AIMD Study.

PubMed

Li, Bing; Ou, Pengfei; Wei, Yulan; Zhang, Xu; Song, Jun

2018-05-03

Density functional theory (DFT) calculations and ab-initio molecular dynamics (AIMD) simulations were performed to understand graphene and its interaction with polycyclic aromatic hydrocarbons (PAHs) molecules. The adsorption energy was predicted to increase with the number of aromatic rings in the adsorbates, and linearly correlate with the hydrophobicity of PAHs. Additionally, the analysis of the electronic properties showed that PAHs behave as mild n-dopants and introduce electrons into graphene; but do not remarkably modify the band gap of graphene, indicating that the interaction between PAHs and graphene is physisorption. We have also discovered highly sensitive strain dependence on the adsorption strength of PAHs onto graphene surface. The AIMD simulation indicated that a sensitive and fast adsorption process of PAHs can be achieved by choosing graphene as the adsorbent. These findings are anticipated to shed light on the future development of graphene-based materials with potential applications in the capture and removal of persistent aromatic pollutants.

A highly sensitive monoclonal antibody based biosensor for quantifying 3-5 ring polycyclic aromatic hydrocarbons (PAHs) in aqueous environmental samples.

PubMed

Li, Xin; Kaattari, Stephen L; Vogelbein, Mary A; Vadas, George G; Unger, Michael A

2016-03-01

Immunoassays based on monoclonal antibodies (mAbs) are highly sensitive for the detection of polycyclic aromatic hydrocarbons (PAHs) and can be employed to determine concentrations in near real-time. A sensitive generic mAb against PAHs, named as 2G8, was developed by a three-step screening procedure. It exhibited nearly uniformly high sensitivity against 3-ring to 5-ring unsubstituted PAHs and their common environmental methylated PAHs, with IC 50 values between 1.68-31 μg/L (ppb). 2G8 has been successfully applied on the KinExA Inline Biosensor system for quantifying 3-5 ring PAHs in aqueous environmental samples. PAHs were detected at a concentration as low as 0.2 μg/L. Furthermore, the analyses only required 10 min for each sample. To evaluate the accuracy of the 2G8-based biosensor, the total PAH concentrations in a series of environmental samples analyzed by biosensor and GC-MS were compared. In most cases, the results yielded a good correlation between methods. This indicates that generic antibody 2G8 based biosensor possesses significant promise for a low cost, rapid method for PAH determination in aqueous samples.

Polycyclic aromatic hydrocarbons in some grounded coffee brands.

PubMed

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

2013-08-01

Potentially toxic 16 priority polycyclic aromatic hydrocarbons (PAHs) were determined in four brands of grounded coffee. Four to 13 PAHs were detected. Concentrations of total PAHs in different brands of coffee samples were in the range of 831.7-1,589.7 μg/kg. Benzo[a]pyrene (2A: probable human carcinogen) was found in Nescafe Premium whereas naphthalene (2B: possible human carcinogen) was found in all the samples of coffee.

Aromatic ring generation as a dust precursor in acetylene discharges

NASA Astrophysics Data System (ADS)

De Bleecker, Kathleen; Bogaerts, Annemie; Goedheer, Wim

2006-04-01

Production of aromatic hydrocarbon compounds as an intermediate step for particle formation in low-pressure acetylene discharges is investigated via a kinetic approach. The detailed chemical reaction mechanism contains 140 reactions among 55 species. The cyclic hydrocarbon chemistry is mainly based on studies of polycyclic aromatic hydrocarbon formation in cosmic environments. The model explicitly includes organic chain, cyclic molecules, radicals, and ions up to a size of 12 carbon atoms. The calculated density profiles show that the aromatic formation yields are quite significant, suggesting that aromatic compounds play a role in the underlying mechanisms of particle formation in hydrocarbon plasmas.

Can Baird's and Clar's Rules Combined Explain Triplet State Energies of Polycyclic Conjugated Hydrocarbons with Fused 4nπ- and (4n + 2)π-Rings?

PubMed

Ayub, Rabia; Bakouri, Ouissam El; Jorner, Kjell; Solà, Miquel; Ottosson, Henrik

2017-06-16

Compounds that can be labeled as "aromatic chameleons" are π-conjugated compounds that are able to adjust their π-electron distributions so as to comply with the different rules of aromaticity in different electronic states. We used quantum chemical calculations to explore how the fusion of benzene rings onto aromatic chameleonic units represented by biphenylene, dibenzocyclooctatetraene, and dibenzo[a,e]pentalene modifies the first triplet excited states (T 1 ) of the compounds. Decreases in T 1 energies are observed when going from isomers with linear connectivity of the fused benzene rings to those with cis- or trans-bent connectivities. The T 1 energies decreased down to those of the parent (isolated) 4nπ-electron units. Simultaneously, we observe an increased influence of triplet state aromaticity of the central 4n ring as given by Baird's rule and evidenced by geometric, magnetic, and electron density based aromaticity indices (HOMA, NICS-XY, ACID, and FLU). Because of an influence of triplet state aromaticity in the central 4nπ-electron units, the most stabilized compounds retain the triplet excitation in Baird π-quartets or octets, enabling the outer benzene rings to adapt closed-shell singlet Clar π-sextet character. Interestingly, the T 1 energies go down as the total number of aromatic cycles within a molecule in the T 1 state increases.

Writing with ring currents: selectively hydrogenated polycyclic aromatics as finite models of graphene and graphane

PubMed Central

Fowler, Patrick W.; Gibson, Christopher M.; Bean, David E.

2014-01-01

Alternating partial hydrogenation of the interior region of a polycyclic aromatic hydrocarbon gives a finite model system representing systems on the pathway from graphene to the graphane modification of the graphene sheet. Calculations at the DFT and coupled Hartree–Fock levels confirm that sp2 cycles of bare carbon centres isolated by selective hydrogenation retain the essentially planar geometry and electron delocalization of the annulene that they mimic. Delocalization is diagnosed by the presence of ring currents, as detected by ipsocentric calculation and visualization of the current density induced in the π system by a perpendicular external magnetic field. These induced ‘ring’ currents have essentially the same sense, strength and orbital origin as in the free hydrocarbon. Subjected to the important experimental proviso of the need for atomic-scale control of hydrogenation, this finding predicts the possibility of writing single, multiple and concentric diatropic and/or paratropic ring currents on the graphene/graphane sheet. The implication is that pathways for free flow of ballistic current can be modelled in the same way. PMID:24611026

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

PubMed Central

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

2015-01-01

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

DIFFUSIVE EXCHANGE OF GASEOUS POLYCYCLIC AROMATIC HYDROCARBONS AND POLYCHLORINATED BIPHENYLS ACROSS THE AIR-WATER INTERFACE OF THE CHESAPEAKE BAY. (R825245)

EPA Science Inventory

Dissolved and gas-phase concentrations of nine polycyclic aromatic hydrocarbons and 46 polychlorinated biphenyl congeners were measured at eight sites on the Chesapeake Bay at four different times of the year to estimate net diffusive air-water gas exchange rates. Gaseous PAHs ar...

Analysis of polycyclic aromatic hydrocarbons in tree-rings of Masson pine (Pinus massoniana L.) from two industrial sites in the Pearl River Delta, south China.

PubMed

Kuang, Yuan-wen; Zhou, Guo-yi; Wen, Da-zhi; Li, Jiong; Sun, Fang-fang

2011-09-01

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were examined and potential sources of PAHs were identified from the dated tree-rings of Masson pine (Pinus massoniana L.) near two industrial sites (Danshuikeng, DSK and Xiqiaoshan, XQS) in the Pearl River Delta of south China. Total concentrations of PAHs (∑PAHs) were revealed with similar patterns of temporal trends in the tree-rings at both sites, suggesting tree-rings recorded the historical variation in atmospheric PAHs. The differences of individual PAHs and of ∑PAHs detected in the tree-rings between the two sites reflected the historical differences of airborne PAHs. Regional changes in industrial activities might contribute to the site-specific and period-specific patterns of the tree-ring PAHs. The diagnostic PAH ratios of Ant/(Ant + PA), FL/(FL + Pyr), and BaA/(BaA + Chr)) revealed that PAHs in the tree-rings at both sites mainly stemmed from the combustion process (pyrogenic sources). Principal component analysis further confirmed that wood burning, coal combustion, diesel, and gasoline-powered vehicular emissions were the dominant contributors of PAHs sources at DSK, while diesel combustion, gasoline and natural gas combustion, and incomplete coal combustion were responsible for the main origins of PAHs at XQS. Tree-ring analysis of PAHs was indicative of PAHs from a mixture of sources of combustion, thus minimizing the bias of short-term active air sampling.

The Phenalenyl Free Radical - a Jahn-Teller D3H PAH

NASA Astrophysics Data System (ADS)

O'Connor, G. D.; Troy, T. P.; Roberts, D. A.; Chalyavi, N.; Fückel, B.; Crossley, M. J.; Nauta, K.; Schmidt, T. W.; Stanton, J. F.

2012-06-01

After benzene and naphthalene, the smallest polycyclic aromatic hydrocarbon bearing six-membered rings is the threefold-symmetric phenalenyl radical. Despite the fact that it is so fundamental, its electronic spectroscopy has not been rigorously scrutinized, in spite of growing interest in graphene fragments for molecular electronic applications. Here we used complementary laser spectroscopic techniques to probe the jet-cooled phenalenyl radical in vacuo. Its spectrum reveals the interplay between four electronic states that exhibit Jahn-Teller and pseudo-Jahn-Teller (Herzberg-Teller) vibronic coupling. The coupling mechanism has been elucidated by the application of various ab initio quantum-chemical techniques.

Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

2015-07-01

An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 μg/L and the limits of quantification ranged from 1.7 to 1550 μg/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Variations in the 6.2 μm emission profile in starburst-dominated galaxies: a signature of polycyclic aromatic nitrogen heterocycles (PANHs)?

NASA Astrophysics Data System (ADS)

Canelo, Carla M.; Friaça, Amâncio C. S.; Sales, Dinalva A.; Pastoriza, Miriani G.; Ruschel-Dutra, Daniel

2018-04-01

Analyses of the polycyclic aromatic hydrocarbon (PAH) feature profiles, especially the 6.2 μm feature, could indicate the presence of nitrogen incorporated in their aromatic rings. In this work, 155 predominantly starburst-dominated galaxies (including H II regions and Seyferts, for example), extracted from the Spitzer/Infrared Spectrograph ATLAS project, have their 6.2 μm profiles fitted allowing their separation into the Peeters' A, B, and C classes. 67 per cent of these galaxies were classified as class A, 31 per cent were as class B, and 2 per cent as class C. Currently, class A sources, corresponding to a central wavelength near 6.22 μm, seem only to be explained by polycyclic aromatic nitrogen heterocycles (PANHs), whereas class B may represent a mix between PAHs and PANHs emissions or different PANH structures or ionization states. Therefore, these spectra suggest a significant presence of PANHs in the interstellar medium (ISM) of these galaxies that could be related to their starburst-dominated emission. These results also suggest that PANHs constitute another reservoir of nitrogen in the Universe, in addition to the nitrogen in the gas phase and ices of the ISM.

Fluorescent aromatic sensors and their methods of use

NASA Technical Reports Server (NTRS)

Meador, Michael A. (Inventor); Tyson, Daniel S. (Inventor); Ilan, Ulvi F. (Inventor)

2012-01-01

Aromatic molecules that can be used as sensors are described. The aromatic sensors include a polycyclic aromatic hydrocarbon core with a five-membered imide rings fused to the core and at least two pendant aryl groups. The aromatic sensor molecules can detect target analytes or molecular strain as a result of changes in their fluorescence, in many cases with on-off behavior. Aromatic molecules that fluoresce at various frequencies can be prepared by altering the structure of the aromatic core or the substituents attached to it. The aromatic molecules can be used as sensors for various applications such as, for example, the detection of dangerous chemicals, biomedical diagnosis, and the detection of damage or strain in composite materials. Methods of preparing aromatic sensor molecules are also described.

Gasoline Particulate Filters as an Effective Tool to Reduce Particulate and Polycyclic Aromatic Hydrocarbon Emissions from Gasoline Direct Injection (GDI) Vehicles: A Case Study with Two GDI Vehicles.

PubMed

Yang, Jiacheng; Roth, Patrick; Durbin, Thomas D; Johnson, Kent C; Cocker, David R; Asa-Awuku, Akua; Brezny, Rasto; Geller, Michael; Karavalakis, Georgios

2018-03-06

We assessed the gaseous, particulate, and genotoxic pollutants from two current technology gasoline direct injection vehicles when tested in their original configuration and with a catalyzed gasoline particulate filter (GPF). Testing was conducted over the LA92 and US06 Supplemental Federal Test Procedure (US06) driving cycles on typical California E10 fuel. The use of a GPF did not show any fuel economy and carbon dioxide (CO 2 ) emission penalties, while the emissions of total hydrocarbons (THC), carbon monoxide (CO), and nitrogen oxides (NOx) were generally reduced. Our results showed dramatic reductions in particulate matter (PM) mass, black carbon, and total and solid particle number emissions with the use of GPFs for both vehicles over the LA92 and US06 cycles. Particle size distributions were primarily bimodal in nature, with accumulation mode particles dominating the distribution profile and their concentrations being higher during the cold-start period of the cycle. Polycyclic aromatic hydrocarbons (PAHs) and nitrated PAHs were quantified in both the vapor and particle phases of the PM, with the GPF-equipped vehicles practically eliminating most of these species in the exhaust. For the stock vehicles, 2-3 ring compounds and heavier 5-6 ring compounds were observed in the PM, whereas the vapor phase was dominated mostly by 2-3 ring aromatic compounds.

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

Forming a Two-Ring Polycyclic Aromatic Hydrocarbon without a Benzene Intermediate: the Reaction of Propargyl with Acetylene

NASA Astrophysics Data System (ADS)

Osborn, David; Savee, John; Selby, Talitha; Welz, Oliver; Taatjes, Craig

The reaction of acetylene (HCCH) with a resonance-stabilized free radical is a commonly invoked mechanism for the generation of polycyclic aromatic hydrocarbons (PAH), which are likely precursors of soot particles in combustion. In this work, we examine the sequential addition of acetylene to the propargyl radical (H2CCCH) at temperatures of 800 and 1000 K. Using time-resolved multiplexed photoionization mass spectrometry with tunable ionizing radiation, we identified the isomeric forms of the C5H5 and C7H7 intermediates in this reaction sequence, and confirmed that the final C9H8 product is the two-ring aromatic compound indene. We identified two different resonance-stabilized C5H5 intermediates, with different temperature dependencies. Furthermore, the C7H7 intermediate is the tropyl radical (c-C7H7) , not the benzyl radical (C6H5CH2) , as is usually assumed in combustion environments. These experimental results are in general agreement with the latest electronic structure / master equation results of da Silva et al. This work shows a pathway for PAH formation that bypasses benzene / benzyl intermediates.

A highly sensitive monoclonal antibody based biosensor for quantifying 3-5 ring polycyclic aromatic hydrocarbons (PAHs) in aqueous environmental samples

PubMed Central

Li, Xin; Kaattari, Stephen L.; Vogelbein, Mary A.; Vadas, George G.; Unger, Michael A.

2016-01-01

Immunoassays based on monoclonal antibodies (mAbs) are highly sensitive for the detection of polycyclic aromatic hydrocarbons (PAHs) and can be employed to determine concentrations in near real-time. A sensitive generic mAb against PAHs, named as 2G8, was developed by a three-step screening procedure. It exhibited nearly uniformly high sensitivity against 3-ring to 5-ring unsubstituted PAHs and their common environmental methylated PAHs, with IC50 values between 1.68–31 μg/L (ppb). 2G8 has been successfully applied on the KinExA Inline Biosensor system for quantifying 3-5 ring PAHs in aqueous environmental samples. PAHs were detected at a concentration as low as 0.2 μg/L. Furthermore, the analyses only required 10 min for each sample. To evaluate the accuracy of the 2G8-based biosensor, the total PAH concentrations in a series of environmental samples analyzed by biosensor and GC-MS were compared. In most cases, the results yielded a good correlation between methods. This indicates that generic antibody 2G8 based biosensor possesses significant promise for a low cost, rapid method for PAH determination in aqueous samples. PMID:26925369

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 (

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.

Polycyclic aromatic hydrocarbons in soils from the Tibetan Plateau, China: distribution and influence of environmental factors.

PubMed

Wang, Shuang; Ni, Hong-Gang; Sun, Jian-Lin; Jing, Xin; He, Jin-Sheng; Zeng, Hui

2013-03-01

Thirty four sampling sites along an elevation transect in the Tibetan Plateau region were chosen. Soil cores were divided into several layers and a total of 175 horizon soil samples were collected from July to September 2011, for determination of polycyclic aromatic hydrocarbons (PAHs). The measured PAHs concentration in surface soils was 56.26 ± 45.84 ng g(-1), and the low molecular weight PAHs (2-3 rings) predominated, accounting for 48% and 35%. We analyzed the spatial (altitudinal and vertical) distribution of PAHs in soil, and explored the influence of related environmental factors. Total organic carbon (TOC) showed a controlling influence on the distribution of PAHs. PAH concentrations declined with soil depth, and the composition patterns of PAHs along soil depth indicated that the heavy PAHs tended to remain in the upper layers (0-10 cm), while the light fractions were transported downward more easily. PAHs inventories (8.77-57.92 mg m(-2)) for soil cores increased with mean annual precipitation, while the topsoil concentrations decreased with it. This implies that an increase in precipitation could transfer more PAHs from the atmosphere to the soil and further transport PAHs from the topsoil to deeper layers.

Determination of polycyclic aromatic hydrocarbon levels of groundwater in Ife north local government area of Osun state, Nigeria.

PubMed

Adekunle, Abolanle Saheed; Oyekunle, John Adekunle Oyedele; Ojo, Oluwaseyi Samson; Maxakato, Nobanathi W; Olutona, Godwin Oladele; Obisesan, Olaoluwa Ruth

2017-01-01

This study determined the presence and levels of Polycyclic Aromatic Hydrocarbons (PAHs) of groundwater in Moro, Edun-Abon, Yakoyo and Ipetumodu communities in Ife-North Local Government Area of Osun State. This was with a view to create public awareness about the safety of groundwater as a source for domestic purposes (e.g., drinking, cooking etc.) in non-industrial area. Water samples were collected on seasonal basis, comprising of three months (August-October) in the wet season and three months (December-February) in the dry season. The PAHs in the water samples were extracted with n -hexane using liquid-liquid extraction method, while their qualitative identifications and quantitative estimations were carried out with the use of gas chromatography. Levels of PAHs detected showed predominance of light PAHs (less than four fused rings) for both wet and the dry seasons. Higher concentrations of PAHs were recorded during the wet season than the dry season. The study concluded that the groundwater in the communities was contaminated with light PAHs and the total PAHs in this area exceeded the maximum permissible limit of 10 μg L -1 recommended by World Health Organization (WHO) for safety of groundwater.

Natural attenuation and biosurfactant-stimulated bioremediation of estuarine sediments contaminated with diesel oil.

PubMed

Bayer, Débora M; Chagas-Spinelli, Alessandra C O; Gavazza, Sávia; Florencio, Lourdinha; Kato, Mario T

2013-09-01

We evaluated the bioremediation, by natural attenuation (NA) and by natural attenuation stimulated (SNA) using a rhamnolipid biosurfactant, of estuarine sediments contaminated with diesel oil. Sediment samples (30 cm) were put into 35 cm glass columns, and the concentrations of the 16 polycyclic aromatic hydrocarbons (PAHs) prioritized by the US Environmental Protection Agency were monitored for 111 days. Naphthalene percolated through the columns more than the other PAHs, and, in general, the concentrations of the lower molecular weight PAHs, consisting of two and three aromatic rings, changed during the first 45 days of treatment, whereas the concentrations of the higher molecular weight PAHs, consisting of four, five, and six rings, were more stable. The higher molecular weight PAHs became more available after 45 days, in the deeper parts of the columns (20-30 cm). Evidence of degradation was observed only for some compounds, such as pyrene, with a total removal efficiency of 82 and 78 % in the NA and SNA treatments, respectively, but without significant difference. In the case of total PAH removal, the efficiencies were significantly different of 82 and 67 %, respectively.

Fungal bioremediation of the creosote-contaminated soil: influence of Pleurotus ostreatus and Irpex lacteus on polycyclic aromatic hydrocarbons removal and soil microbial community composition in the laboratory-scale study.

PubMed

Byss, Marius; Elhottová, Dana; Tříska, Jan; Baldrian, Petr

2008-11-01

The aim of this study was to determine the efficacy of selected basidiomycetes in the removing of polycyclic aromatic hydrocarbons (PAH) from the creosote-contaminated soil. Fungi Pleurotus ostreatus and Irpex lacteus were supplemented with creosote-contaminated (50-200 mg kg(-1) PAH) soil originating from a wood-preserving plant and incubated at 15 °C for 120 d. Either fungus degraded PAH with 4-6 aromatic rings more efficiently than the microbial community present initially in the soil. PAH removal was higher in P. ostreatus treatments (55-67%) than in I. lacteus treatments (27-36%) in general. P. ostreatus (respectively, I. lacteus) removed 86-96% (47-59%) of 2-rings PAH, 63-72% (33-45%) of 3-rings PAH, 32-49% (9-14%) of 4-rings PAH and 31-38% (11-13%) of 5-6-rings PAH. MIS (Microbial Identification System) Sherlock analysis of the bacterial community determined the presence of dominant Gram-negative bacteria (G-) Pseudomonas in the inoculated soil before the application of fungi. Complex soil microbial community was characterized by phospholipid fatty acids analysis followed by GC-MS/MS. Either fungus induced the decrease of bacterial biomass (G- bacteria in particular), but the soil microbial community was influenced by P. ostreatus in a different way than by I. lacteus. The bacterial community was stressed more by the presence of I. lacteus than P. ostreatus (as proved by the ratio of the fungal/bacterial markers and by the ratio of trans/cis mono-unsaturated fatty acids). Moreover, P. ostreatus stimulated the growth of Gram-positive bacteria (G+), especially actinobacteria and these results indicate the potential of the positive synergistic interaction of this fungus and actinobacteria in creosote biodegradation.

On the role of resonantly stabilized radicals in polycyclic aromatic hydrocarbon (PAH) formation: pyrene and fluoranthene formation from benzyl-indenyl addition.

PubMed

Sinha, Sourab; Rahman, Ramees K; Raj, Abhijeet

2017-07-26

Resonantly stabilized radicals, such as propargyl, cyclopentadienyl, benzyl, and indenyl, play a vital role in the formation and growth of polycyclic aromatic hydrocarbons (PAHs) that are soot precursors in engines and flames. Pyrene is considered to be an important PAH, as it is thought to nucleate soot particles, but its formation pathways are not well known. This paper presents a reaction mechanism for the formation of four-ring aromatics, pyrene and fluoranthene, through the combination of benzyl and indenyl radicals. The intermediate species and transition structures involved in the elementary reactions of the mechanism were studied using density functional theory, and the reaction kinetics were evaluated using transition state theory. The barrierless addition of benzyl and indenyl to form the adduct, 1-benzyl-1H-indene, was found to be exothermic with a reaction energy of 204.2 kJ mol -1 . The decomposition of this adduct through H-abstraction and H 2 -loss was studied to determine the possible products. The rate-of-production analysis was conducted to determine the most favourable reactions for pyrene and fluoranthene formation. The premixed laminar flames of toluene, ethylbenzene, and benzene were simulated using a well-validated hydrocarbon fuel mechanism with detailed PAH chemistry after adding the proposed reactions to it. The computed and experimentally observed species profiles were compared to determine the effect of the new reactions for pyrene and fluoranthene formation on their concentration profiles. The role of benzyl and indenyl combination in PAH formation and growth is highlighted.

Determination of particle-bound polycyclic aromatic hydrocarbons emitted from co-pelletization combustion of lignite and rubber wood sawdust

NASA Astrophysics Data System (ADS)

Kan, R.; Kaosol, T.; Tekasakul, P.; Tekasakul, S.

2017-09-01

Determination of particle-bound Polycyclic Aromatic Hydrocarbons (PAHs) emitted from co-pelletization combustion of lignite and rubber wood sawdust in a horizontal tube furnace is investigated using High Performance Liquid Chromatography with coupled Diode Array and Fluorescence Detection (HPLC-DAD/FLD). The particle-bound PAHs based on the mass concentration and the toxicity degree are discussed in the different size ranges of the particulate matters from 0.07-11 μm. In the present study, the particle-bound PAHs are likely abundant in the fine particles. More than 70% of toxicity degree of PAHs falls into PM1.1 while more than 80% of mass concentration of PAHs falls into PM2.5. The addition of lignite amount in the co-pelletization results in the increasing concentration of either 4-6 aromatic ring PAHs or high molecular weight PAHs. The high contribution of 4-6 aromatic ring PAHs or high molecular weight PAHs in the fine particles should be paid much more attention because of high probability of human carcinogenic. Furthermore, the rubber wood sawdust pellets emit high mass concentration of PAHs whereas the lignite pellets emit high toxicity degree of PAHs. By co-pelletized rubber wood sawdust with lignite (50% lignite pellets) has significant effect to reduce the toxicity degree of PAHs by 70%.

INTERACTION OF PAH-RELATED COMPOUNDS WITH THE ALPHA AND BETA ISOFORMS OF ESTROGEN RECEPTOR. (R826192)

EPA Science Inventory

The ability of several 4- and 5-ring polycyclic aromatic hydrocarbons (PAHs), heterocyclic PAHs, and their monohydroxy derivatives to interact with the estrogen receptor (ER) alpha and beta isoforms was examined. Only compounds possessing a hydroxyl group were able to compete wit...

The study of azaarene behavior over atmosphere of subtropical city(Keelung)

NASA Astrophysics Data System (ADS)

Liu, Chih Yun

2017-04-01

In this study, we collected the Total Suspended Particulates (TSP) from July 2014 to February 2016 in the subtropical city (Keelung), and researched azaarene behavior over atmosphere. Polycyclic Aromatic Compounds (PAHs) are ubiquitous pollutants in the environment; they have known carcinogens and/or mutagens, mainly produce from incomplete combustion. Azaarenes are polycyclic aromatic hydrocarbon derivative compounds in which a carbon atom in one of the aromatic rings is substituted by a nitrogen atom. Organism exposure to azaarenes occurs through inhalation of polluted air and by ingestion of food and/or water containing combustion products and accumulate in the body. Total azaarene concentration (16 individual compound concentration of the aggregate) is between 0.92 to 3.76 μg/m3, results showed that the concentration of azaarenes have significant seasonal variation, they have higher concentration in the cold month. In molecular weight, the highest proportion is the molecular weight equal to 143(ΣMQ) and then the molecular weight equal to 179(BAP), ΣMQ would rise from 30% 40% to 40% 50% during the cold month and warm months. Compared to ring number, 2-rings are biggest part, the smallest is 4-rings, its ratio has slight variation, but primary species is 2-rings. Emissions from transportation, local housing heating, factories burning fossil fuels and dust from Mainland south air mass are pollutant, their sources and climate conditions can affect concentration and composition of compound. There are highly significant correlation between 3-rings and 4-rings, which suggests that there are similar source strengths and transport mechanisms for these compounds. Correlation between concentration of azaarenes and ambient temperature is negative moderation, with concentration of atmospheric suspended particles is positive moderate correlation. Finally, we establish the relationship between the three parameters to predict concentration of azaarenes over atmosphere of subtropical regions. Key words: azaarenes, atmospheric suspended particles, subtropical city, multiple regression analysis.

Distribution of polycyclic aromatic hydrocarbons in southern Chesapeake Bay surface water: Evaluation of three methods for determining freely dissolved water concentrations

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

Gustafson, K.E.; Dickhut, R.M.

1997-03-01

Gas sparging, semipermeable-membrane devices (SPMDs), and filtration with sorption of dissolved polycyclic aromatic hydrocarbons (PAHs) to XAD-2 resin were evaluated for determining the concentrations of freely dissolved PAHs in estuarine waters of southern Chesapeake Bay at sites ranging from rural to urban and highly industrialized. Gas sparging had significant sampling artifacts due to particle scavenging by rising bubbles, and SPMDs were kinetically limited for four-ring and larger PAHs relative to short-term temporal changes in water concentrations. Filtration with sorption of the dissolved contaminant fraction to XAD-2 resin was found to be the most accurate and feasible method for determining concentrationsmore » of freely dissolved PAHs in estuarine water. Concentrations and distribution coefficients of dissolved and particulate PAHs were measured using the filtration/XAD-2 method. Concentrations of PAHs in surface waters of southern Chesapeake Bay were higher than those reported for the northern bay; concentrations in the Elizabeth River were elevated relative to all other sites. A gradient for particulate PAHs was observed from urban to remote sites. No seasonal trends were observed in dissolved or particle-bound PAH fractions at any site. Distributions of dissolved and particulate PAHs in surface waters of the Chesapeake Bay are near equilibrium at all locations and during all seasons.« less

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

PubMed Central

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

2000-01-01

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

Laboratory Studies of Stabilities of Heterocyclic Aromatic Molecules: Suggested Gas Phase Ion-Molecule Routes to Production in Interstellar Gas Clouds

NASA Technical Reports Server (NTRS)

Adams, Nigel G.; Fondren, L. Dalila; McLain, Jason L.; Jackson, Doug M.

2006-01-01

Several ring compounds have been detected in interstellar gas clouds, ISC, including the aromatic, benzene. Polycyclic aromatic hydrocarbons, PAHs, have been implicated as carriers of diffuse interstellar bands (DIBs) and unidentified infrared (UIR) bands. Heterocyclic aromatic rings of intermediate size containing nitrogen, possibly PreLife molecules, were included in early searches but were not detected and a recent search for Pyrimidine was unsuccessful. Our laboratory investigations of routes to such molecules could establish their existence in ISC and suggest conditions under which their concentrations would be maximized thus aiding the searches. The stability of such ring compounds (C5H5N, C4H4N2, C5H11N and C4H8O2) has been tested in the laboratory using charge transfer excitation in ion-molecule reactions. The fragmentation paths, including production of C4H4(+), C3H3N(+) and HCN, suggest reverse routes to the parent molecules, which are presently under laboratory investigation as production sources.

Polycyclic aromatic hydrocarbons (PAHs) in water from three estuaries of China: Distribution, seasonal variations and ecological risk assessment.

PubMed

Yan, Jinxia; Liu, Jingling; Shi, Xuan; You, Xiaoguang; Cao, Zhiguo

2016-08-15

The distribution, seasonal variations and ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in water from three estuaries in Hai River Basin of China, which has been suffering from different anthropogenic pressures, were investigated. In three estuaries, the average concentration of ΣPAHs was the lowest in Luan River estuary, followed by Hai River estuary, and the highest in Zhangweixin River estuary. There were significant seasonal variations in ΣPAHs, the concentrations of ΣPAHs were higher in November than in May and August. The composition profiles of PAHs in different sites were significantly different, and illustrated seasonal variations. Generally, 2-ring (Nap) and 3-ring PAHs (Acp, Fl and Phe) were the most abundant components at most sampling sites in three estuaries. The PAHs in three estuaries were mainly originated from pyrogenic sources. A method based on toxic equivalency factors (TEFs) and risk quotient (RQ) was proposed to assess the ecological risk of ΣPAHs, with the ecological risk of individual PAHs being considered separately. The results showed that the ecological risks caused by ΣPAHs were high in Hai River estuary and Zhangweixin River estuary, and moderate in Luan River estuary. The mean values of ecological risk in August were lower than those in November. The contributions of individual PAHs to ecological risk were different in May, August and November. 3-ring and 4-ring PAHs accounted for much more ecological risk than 2-ring, 5-ring and 6-ring, although the contributions of 5-ring and 6-ring to ecological risk were higher than these to PAHs concentrations. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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

2006-02-15

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

[Pollution characteristics and sources of polycyclic aromatic hydrocarbons in urban rivers of Wenzhou city].

PubMed

Zhou, Jie-Cheng; Chen, Zhen-Lou; Bi, Chun-Juan; Lü, Jin-Gang; Xu, Shi-Yuan; Pan, Qi

2012-12-01

Concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) in water and surface sediments collected from the urban rivers of Wenzhou city in spring and summer were measured by GC-MS. The results showed that the total PAHs concentrations in water and sediments of the studied rivers varied in ranges of 146.74-3 047.89 ng x L(-1) and 21.01-11 990.48 ng x g(-1), respectively. Higher concentrations occurred in spring. The low and middle rings of 2-4-ring were dominant in both water and sediments, but the concentrations of 5-ring and 6-ring PAHs in sediments were relatively higher than those in water. The EBaP values of PAHs in water of the studied rivers in spring and summer were 1.69-51.95 ng x L(-1) and 0-3.03 ng x L(-1), respectively. Eighty percent of water samples in spring surpassed the limits of BaP in surface water of China. The concentrations of sigma PAHs in the sediments both in spring and summer were lower than the ERM value, but part of the components of PAHs had values higher than the ERM, suggesting possible toxic effect on living organisms. Based on the PAHs molecule ratios and principal component analysis, a mixed PAHs source of petroleum and combustion in water and sediments was diagnosed, while sediments showed a greater proportion of combustion sources.

Variations in the bioavailability of polycyclic aromatic hydrocarbons in industrial and agricultural soils after bioremediation.

PubMed

Guo, Meixia; Gong, Zongqiang; Allinson, Graeme; Tai, Peidong; Miao, Renhui; Li, Xiaojun; Jia, Chunyun; Zhuang, Jie

2016-02-01

The aim of this study was to demonstrate the variations in bioavailability remaining in industrial and agricultural soils contaminated by polycyclic aromatic hydrocarbons (PAHs) after bioremediation. After inoculation of Mycobacterium sp. and Mucor sp., PAH biodegradation was tested on a manufactured gas plant (MGP) soil and an agricultural soil. PAH bioavailability was assessed before and after biodegradation using solid-phase extraction (Tenax-TA extraction) and solid-phase micro-extraction (SPME) to represent bioaccessibility and chemical activity of PAHs, respectively. Only 3- and 4-ring PAHs were noticeably biodegradable in the MGP soil. PAH biodegradation in the agricultural soil was different from that in the MGP soil. The rapidly desorbing fractions (F(rap)) extracted by Tenax-TA and the freely dissolved concentrations of 3- and 4-ring PAHs determined by SPME from the MGP soil decreased after 30 days biodegradation; those values of the 5- and 6-ring PAHs changed to a lesser degree. For the agricultural soil, the F(rap) values of the 3- and 4-ring PAHs also decreased after the biodegradation experiment. The Tenax-TA extraction and the SPME have the potential to assess variations in the bioavailability of PAHs and the degree of biodegradation in contaminated MGP soils. In addition, Tenax-TA extraction is more sensitive than SPME when used in the agricultural soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Long term trends in atmospheric concentrations of polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons: A study of Japanese cities from 1997 to 2014.

PubMed

Hayakawa, Kazuichi; Tang, Ning; Nagato, Edward Gou; Toriba, Akira; Sakai, Shigekatsu; Kano, Fumio; Goto, Sumio; Endo, Osamu; Arashidani, Kei-Ichi; Kakimoto, Hitoshi

2018-02-01

Total suspended particulate matter (TSP) was collected during the summer and winter in five Japanese cities spanning Hokkaido to Kyushu (Sapporo, Kanazawa, Tokyo, Sagamihara and Kitakyushu) from 1997 to 2014. Nine polycyclic aromatic hydrocarbons (PAHs) with four to six rings, including pyrene (Pyr) and benzo[a]pyrene (BaP), were identified using high-performance liquid chromatography (HPLC) with fluorescence detection. Two nitropolycyclic aromatic hydrocarbons (NPAHs), 1-nitropyrene (1-NP) and 6-nitrobenzo[a]pyrene (6-NBaP), were identified by HPLC with chemiluminescence detection. A comparison of PAH and NPAH concentrations and [NPAH]/[PAH] ratios such as [1-NP]/[Pyr] and [6-NBaP]/[BaP] revealed the following characteristics in the five cities: (1) In Sapporo, Kanazawa, Tokyo and Sagamihara, the concentrations of PAHs and NPAHs were high at the beginning of the sampling period and then steadily decreased, with NPAHs decreasing faster than PAHs. The large initial [1-NP]/[Pyr] ratios suggest that the major contributor was automobiles but subsequent decreases in this ratio suggest decreased automobile contributions. (2) By contrast, PAH concentrations in Kitakyushu did not decrease during the sampling period, though concentrations of NPAHs decreased. The consistently smaller [1-NP]/[Pyr] ratio and larger [6-NBaP]/[BaP] ratio in Kitakyushu suggests that the major contributor of PAHs was not automobiles but iron manufacturing which uses a large amount of coal. The sudden increase in atmospheric PAH concentrations in the winter of 2014 may also be due to iron manufacturing. Copyright © 2017 Elsevier Ltd. All rights reserved.

Release behavior and formation mechanism of polycyclic aromatic hydrocarbons during coal pyrolysis.

PubMed

Gao, Meiqi; Wang, Yulong; Dong, Jie; Li, Fan; Xie, Kechang

2016-09-01

Polycyclic aromatic hydrocarbons (PAHs) are major environmental pollutants. They have attracted considerable attention due to their severe potential carcinogenic, mutagenic and genotoxic effects on human health. In this study, five different rank coals from China were pyrolyzed using pyro-probe CDS 5250 and the release behavior of 16 PAHs under different pyrolysis conditions were studied by Gas Chromatography-Mass Spectrometer (GC-MS). The structural characteristics of the five coals were determined by Cross-Polarization/Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS (13)C NMR) spectroscopy, and then the factors influencing the formation of PAHs during coal pyrolysis were discussed together with the coal structural data. It was shown that the amount of PAHs generated during coal pyrolysis was largely related to coal rank and followed the order of medium metamorphic coal > low metamorphic coal > high metamorphic coal. The amount of total PAHs varied as the temperature was increased from 400 °C to 1200 °C, which showed a trend of first increasing and then decreasing, with the maximum value at 800 °C. Moreover, the species of PAHs released varied with pyrolysis temperatures. When the temperature was lower than 800 °C, the small ring PAHs were the most abundant, while the proportion of heavy rings increased at higher temperature. The results indicate that the formation of PAHs during coal pyrolysis depends on the structure of the coal. The species and amounts of PAHs generated during coal pyrolysis are closely related to the contents of protonated aromatic carbons and bridging ring junction aromatic carbons present in the coal structure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Contaminated sediments from tributaries of the Great Lakes: Chemical characterization and carcinogenic effects in medaka (Oryzias latipes)

USGS Publications Warehouse

Besser, John M.; Schmitt, Christopher J.; Harshbarger, John C.; Peterman, Paul H.; Lebo, Jon A.

1991-01-01

Sediments from four inshore industrial sites and a reference site in the Great Lakes were extracted with organic solvents to produce a crude extract, which was separated on alumina into two fractions: predominantly polycyclic aromatic hydrocarbons; and predominantly nitrogencontaining polycyclic aromatic compounds. Crude extracts were redissolved in acetone and analyzed by gas chromatography and gas chromatography-mass spectrometry. The acetone-redissolved crude extracts from the four industrialized sites contained 5.6–313.3 μg total polycyclic aromatic compounds/g sediment and 3.0–36.4 μg other compounds/g sediment. In addition to the typical EPA priority pollutants, a substantial amount (228.7 μg/g sediment) of alkyl-polycyclic-aromatic compounds was detected in sediments from one of the industrialized sites. Extracts from the reference site contained 1.55 μg total polycyclic aromatic compounds/ g sediment. Medaka (Oryzias latipes) were exposed to multiple pulse doses of acetone-redissolved extracts and fractions. Medaka were also exposed to a known carcinogen, methylazoxymethanol acetate, to verify that chemicals produced tumors in the test fish. Acetone-redissolved extracts and fractions from contaminated sediments were toxic to medaka. Fin erosion and non-neoplastic liver abnormalities were more prevalent in medaka after exposure to acetoneredissolved extracts and fractions from contaminated sediments. Neoplasms previously associated with chemical exposure in wild fishes were induced in medaka exposed to acetone-redissolved extracts and fractions from two of the contaminated sites, but not from the reference site or controls. These findings further support the hypothesis that chemical contaminants in sediments are involved in epizootics of neoplasms in wild fishes at contaminated sites.

CLONING AND CHARACTERIZATION OF THE PHTHALATE CATABOLISM REGION OF PRE1 OF ARTHROBACTER KEYSERI 12B

EPA Science Inventory

o-Phthalate (benzene-1,2-dicarboxylate) is a central intermediate in the bacterial degradation of phthalate ester plasticizers as well as of a number of fused-ring polycyclic aromatic hydrocarbons found in fossil fuels. In Arthrobacter keyseri 12B, the genes encoding catabolism o...

Size-dependent distribution and inhalation cancer risk of particle-bound polycyclic aromatic hydrocarbons at a typical e-waste recycling and an urban site.

PubMed

Luo, Pei; Bao, Lian-Jun; Li, Shao-Meng; Zeng, Eddy Y

2015-05-01

Atmospheric particle size distribution of polycyclic aromatic hydrocarbons (PAHs) in a typical e-waste recycling zone and an urban site (Guangzhou) in southern China featured a unimodal peak in 0.56-1.8 μm for 4-6 ring PAHs but no obvious peak for 2-3 ring PAHs at both sites. The atmospheric deposition fluxes of PAHs were estimated at 5.4 ± 2.3 μg m(-2) d(-1) in the e-waste recycling zone and 3.1 ± 0.6 μg m(-2) d(-1) in Guangzhou. In addition, dry and wet deposition fluxes of PAHs were dominated by coarse (Dp > 1.8 μm) and fine particles (Dp < 1.8 μm), respectively. Fine particles predominated the deposition of PAHs in the lung. The results estimated by incremental inhalation cancer risk suggested that particle-bound PAHs posed serious threat to human health within the e-waste recycling zone and Guangzhou. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sedimentary records of polycyclic aromatic hydrocarbons (PAHs) in remote lakes across the Tibetan Plateau.

PubMed

Yang, Ruiqiang; Xie, Ting; Li, An; Yang, Handong; Turner, Simon; Wu, Guangjian; Jing, Chuanyong

2016-07-01

Sediment cores from five lakes across the Tibetan Plateau were used as natural archives to study the time trends of polycyclic aromatic hydrocarbons (PAHs). The depositional flux of PAHs generally showed an increasing trend from the deeper layers towards the upper layer sediments. The fluxes of PAHs were low with little variability before the 1950s, and then gradually increased to the late 1980s, with a faster increasing rate after the 1990s. This temporal pattern is clearly different compared with those remote lakes across the European mountains when PAHs started to decrease during the period 1960s-1980s. The difference of the temporal trend was attributed to differences in the economic development stages and energy structure between these regions. PAHs are dominated by the lighter 2&3-ring homologues with the averaged percentage over 87%, while it is notable that the percentage of heavier 4-6 ring PAHs generally increased in recent years, which suggests the contribution of local high-temperature combustion sources becoming more predominant. Copyright © 2016 Elsevier Ltd. All rights reserved.

Partitioning studies of coal-tar constituents in a two-phase contaminated ground-water system

USGS Publications Warehouse

Rostad, C.E.; Pereira, W.E.; Hult, M.F.

1985-01-01

Organic compounds derived from coal-tar wastes in a contaminated aquifer in St. Louis Park, Minnesota, were identified, and their partition coefficients between the tar phase and aqueous phase were determined and compared with the corresponding n-octanol/water partition coefficients. Coal tar contains numerous polycyclic aromatic compounds, many of which are suspected carcinogens or mutagens. Groundwater contamination by these toxic compounds may pose an environmental health hazard in nearby public water-supply wells. Fluid samples from this aquifer developed two phases upon settling: an upper aqueous phase, and a lower oily-tar phase. After separating the phases, polycyclic aromatic compounds in each phase were isolated using complexation with N-methyl-2-pyrrolidone and identified by fused-silica capillary gas chromatography/mass spectrometry. Thirty-one of the polycyclic aromatic compounds were chosen for further study from four different classes: 12 polycyclic aromatic hydrocarbons, 10 nitrogen heterocycles, 5 sulfur heterocycles, and 4 oxygen heterocycles. Within each compound class, the tar/water partition coefficients of these compounds were reasonably comparable with the respective n-octanol/water partition coefficient.

Polycyclic aromatic hydrocarbons assessment in sediment of national parks in southeast Brazil.

PubMed

Meire, Rodrigo Ornellas; Azeredo, Antonio; Pereira, Márcia de Souza; Torres, João Paulo Machado; Malm, Olaf

2008-08-01

The aim of this work was to assess the levels of polycyclic aromatic hydrocarbons (PAHs) in the environment and their sources found in protected regions of southeastern Brazil. Samples of sediments were collected at four National Parks: Itatiaia National Park (PNIT), Serra da Bocaina National Park (PNSB), Serra dos Orgãos National Park (PNSO) and Jurubatiba National Park (PNJUB). The National Parks studied comprise rainforests, altitudinal fields and 'restinga' environments located in the Minas Gerais, Rio de Janeiro and São Paulo states. The sampling was conducted between 2002 and 2004 from June to September. In general, the environmental levels of PAHs found were similar to those in other remote areas around the globe. PNIT exhibited the highest median values of total PAHs in sediment (97 ng g(-1)), followed by PNJUB (89 ng g(-1)), PNSO (57 ng g(-1)) and PNSB (27 ng g(-1)). The highest levels of total PAHs (576 and 24430 ng g(-1)) could be associated to a point source contamination where are characterized for human activities. At PNSB and PNIT the PAH profiles were richer in 2 and 3 ring compounds, whereas at PNSO and PNJUB, the profiles exhibited 3 and 4 ring compounds. The phenanthrene predominance in most samples could indicate the influence of biogenic synthesis. The samples with a petrogenic pattern found in this study might be associated with the vicinity of major urban areas, highway traffic and/or industrial activities close to PNSO and PNIT. At PNIT and PNJUB, forest fires and slash and burn agricultural practices may drive the results towards a pyrolytic pattern.

Effect through inhalation on human health of PM1 bound polycyclic aromatic hydrocarbons collected from foggy days in northern part of India.

PubMed

Singh, Dharmendra Kumar; Gupta, Tarun

2016-04-05

We investigated the health risk from 16 polycyclic aromatic hydrocarbons (PAHs) adsorbed on submicron particles and also reported their concentrations, spatial distribution and possible sources during foggy days at Kanpur. Twenty-four urban foggy day's samples gathered from Kanpur, an urban center in North India and most densely populated city in the Indo-Gangetic plain of India, were examined for 16 PAHs (2-6 rings).The mean concentration of PM1 was found to be 160.16±37.70μg/m(3). ∑16PAHs concentrations were 529.17ng/m(3) with a mean of 33.07ng/m(3). The compounds of higher molecular weight (4-6 rings) added to 70.67% of ∑PAHs mass concentration in the foggy day's samples. The results of source identification by using principle component analysis (PCA) and diagnostic ratios proposed that the primary sources of PAHs were vehicular emission (primarily driven by diesel fuel) and coal combustion and the secondary source. Exposure to total PAHs in the ambient air resulted in, 95% probability total Incremental Lifetime Cancer Risk (TILCR) 3.57×10(-5) for adults and 2.08×10(-5) for children or (∼35 cancer case per million in adults and ∼20 cancer case per million in children) due to inhalation in terms of ILCR were higher than the baseline value of acceptable risk (one cancer case per million people) suggesting moderate health risk to resident human population. Copyright © 2015 Elsevier B.V. All rights reserved.

Water quality concerns due to forest fires: polycyclic aromatic hydrocarbons (PAH) contamination of groundwater from mountain areas.

PubMed

Mansilha, C; Carvalho, A; Guimarães, P; Espinha Marques, J

2014-01-01

Water quality alterations due to forest fires may considerably affect aquatic organisms and water resources. These impacts are cumulative as a result of pollutants mobilized from fires, chemicals used to fight fire, and postfire responses. Few studies have examined postfire transport into water resources of trace elements, including the polycyclic aromatic hydrocarbons (PAH), which are organic pollutants produced during combustion and are considered carcinogenic and harmful to humans. PAH are also known to adversely affect survival, growth, and reproduction of many aquatic species. This study assessed the effects of forest wildfires on groundwater from two mountain regions located in protected areas from north and central Portugal. Two campaigns to collect water samples were performed in order to measure PAH levels. Fifteen of 16 studied PAH were found in groundwater samples collected at burned areas, most of them at concentrations significantly higher than those found in control regions, indicating aquifer contamination. The total sum of PAH in burned areas ranged from 23.1to 95.1 ng/L with a median of 62.9 ng/L, which is one- to sixfold higher than the average level measured in controls (16.2 ng/L). In addition, in control samples, the levels of light PAH with two to four rings were at higher levels than heavy PAH with five or six rings, thus showing a different profile between control and burned sites. The contribution of wildfires to groundwater contamination by PAH was demonstrated, enabling a reliable assessment of the impacts on water quality and preparation of scientifically based decision criteria for postfire forest management practices.

Emission, distribution and toxicity of polycyclic aromatic hydrocarbons (PAHs) during municipal solid waste (MSW) and coal co-combustion.

PubMed

Peng, Nana; Li, Yi; Liu, Zhengang; Liu, Tingting; Gai, Chao

2016-09-15

Emission and distribution characteristics of polycyclic aromatic hydrocarbons (PAHs) were investigated during municipal solid waste (MSW) and coal combustion alone and MSW/coal blend (MSW weight fraction of 25%) co-combustion within a temperature range of 500°C-900°C. The results showed that for all combustion experiments, flue gas occupied the highest proportion of total PAHs and fly ash contained more high-ring PAHs. Moreover, the 3- and 4-ring PAHs accounted for the majority of total PAHs and Ant or Phe had the highest concentrations. Compared to coal, MSW combustion generated high levels of total PAHs with the range of 111.28μg/g-10,047.22μg/g and had high toxicity equivalent value (TEQ). MSW/coal co-combustion generated the smallest amounts of total PAHs and had the lowest TEQ than MSW and coal combustion alone. Significant synergistic interactions occurred between MSW and coal during co-combustion and the interactions suppressed the formation of PAHs, especially hazardous high-ring PAHs and decreased the TEQ. The present study indicated that the reduction of the yield and toxicity of PAHs can be achieved by co-combustion of MSW and coal. Copyright © 2016 Elsevier B.V. All rights reserved.

Groundwater contamination by polycyclic aromatic hydrocarbon due to diesel spill from a telecom base station in a Nigerian City: assessment of human health risk exposure.

PubMed

Ugochukwu, Uzochukwu Cornelius; Ochonogor, Alfred

2018-03-26

Diesel pollution of groundwater poses great threat to public health, mainly as a result of the constituent polycyclic aromatic hydrocarbons (PAHs). In this study, the human health risk exposure to polycyclic aromatic hydrocarbons (PAHs) in diesel contaminated groundwater used by several families at Ring Road, Jos, Nigeria (as caused by diesel spill from a telecom base station) was assessed. Prior to the groundwater being treated, the residents were using the water after scooping off the visible diesel sheen for purposes of cooking, washing, and bathing. Until this study, it is not clear whether the groundwater contamination had resulted in sub-chronic exposure of the residents using the water to polycyclic aromatic hydrocarbons (PAHs) to the extent of the PAHs posing a health risk. The diesel contaminated groundwater and uncontaminated nearby groundwater (control) were collected and analyzed for PAHs using gas chromatography-mass spectrometry (GC-MS). The dosage of the dermal and oral ingestion entry routes of PAHs was determined. The estimation of the non-carcinogenic health risk was via hazard quotients (HQ) and the associated hazard index (HI), while the estimation of the carcinogenic health risk was via lifetime cancer risks (LCR) and the associated risk index (RI). Obtained results indicate that the exposure of the residents to the PAHs may have made them susceptible to the risk of non-carcinogenic health effects of benzo(a)pyrene and the carcinogenic health effects of benzo(a)anthracene and benzo(a)pyrene.

Proteomic Characterization of Plasmid pLA1 for Biodegradation of Polycyclic Aromatic Hydrocarbons in the Marine Bacterium, Novosphingobium pentaromativorans US6-1

PubMed Central

Yun, Sung Ho; Choi, Chi-Won; Lee, Sang-Yeop; Lee, Yeol Gyun; Kwon, Joseph; Leem, Sun Hee; Chung, Young Ho; Kahng, Hyung-Yeel; Kim, Sang Jin; Kwon, Kae Kyoung; Kim, Seung Il

2014-01-01

Novosphingobium pentaromativorans US6-1 is a halophilic marine bacterium able to degrade polycyclic aromatic hydrocarbons (PAHs). Genome sequence analysis revealed that the large plasmid pLA1 present in N. pentaromativorans US6-1 consists of 199 ORFs and possess putative biodegradation genes that may be involved in PAH degradation. 1-DE/LC-MS/MS analysis of N. pentaromativorans US6-1 cultured in the presence of different PAHs and monocyclic aromatic hydrocarbons (MAHs) identified approximately 1,000 and 1,400 proteins, respectively. Up-regulated biodegradation enzymes, including those belonging to pLA1, were quantitatively compared. Among the PAHs, phenanthrene induced the strongest up-regulation of extradiol cleavage pathway enzymes such as ring-hydroxylating dioxygenase, putative biphenyl-2,3-diol 1,2-dioxygenase, and catechol 2,3-dioxygenase in pLA1. These enzymes lead the initial step of the lower catabolic pathway of aromatic hydrocarbons through the extradiol cleavage pathway and participate in the attack of PAH ring cleavage, respectively. However, N. pentaromativorans US6-1 cultured with p-hydroxybenzoate induced activation of another extradiol cleavage pathway, the protocatechuate 4,5-dioxygenase pathway, that originated from chromosomal genes. These results suggest that N. pentaromativorans US6-1 utilizes two different extradiol pathways and plasmid pLA1 might play a key role in the biodegradation of PAH in N. pentaromativorans US6-1. PMID:24608660

[Polycyclic aromatic hydrocarbons (PAHs) in herbs and fruit teas].

PubMed

Ciemniak, Artur

2005-01-01

Polycyclic aromatic hydrocarbons (PAHs) of which benzo[a]pyrene is the most commonly studied and measured, are fused - ring aromatic compounds formed in both natural and man made processes and are found widely distributed throughout the human environment. PAHs occur as contaminants in different food categories and beverages including water, vegetables, fruit, cereals, oils and fats, barbecued and smoked meat. The sources of PAHs in food are predominantly from environmental pollution and food processing. PAHs emissions from automobile traffic and industry activities were show to influence the PAHs levels in vegetables and fruits. The present study was carried out to determine levels of 16 basic PAHs in herbs and fruit teas. The method was based on the hexane extraction and cleaned up by florisil cartridge. The extracts were analysed by GC-MS. The levels of total PAHs varied from 48,27 microg/kg (hibiscus tea) to 1703 microg/kg (green tea). The highest level of BaP was found in lime tea (74,2 microg/kg).

The distribution and sources of polycyclic aromatic hydrocarbons in shallow groundwater from an alluvial-diluvial fan of the Hutuo River in North China

NASA Astrophysics Data System (ADS)

Wang, Jincui; Zhao, Yongsheng; Sun, Jichao; Zhang, Ying; Liu, Chunyan

2018-06-01

This paper has investigated the concentration and distribution of polycyclic aromatic hydrocarbons in shallow groundwater from an alluvial-diluvial fan of the Hutuo River in North China. Results show that the concentration levels of 16 priority polycyclic aromatic hydrocarbons range from 0 to 92.06 ng/L, do not conform to drinking water quality standards in China (GB 5749- 2006). However, the concentration figures of priority polycyclic aromatic hydrocarbons are much lower than that of other studies conducted elsewhere in China. In addition, highly-concentrated polycyclic aromatic hydrocarbons (50-92 ng/L) are fragmentarily distributed. The composition of polycyclic aromatic hydrocarbons from this study indicates that low molecular polycyclic aromatic hydrocarbons are predominant in groundwater samples, medium molecular compounds occur at low concentrations, and high molecular hydrocarbons are not detected. The polycyclic aromatic hydrocarbon composition in groundwater samples is basically the same as that of gaseous samples in the atmosphere in this study. Therefore, the atmospheric input is assumed to be an important source of polycyclic aromatic hydrocarbons, no less than wastewater discharge, adhesion on suspended solids, and surface water leakage. Ratios of specific polycyclic aromatic hydrocarbons demonstrate that they mainly originate from wood or coal combustion as well as natural gas and partially from petroleum according to the result of principal component analysis. On the whole, conclusions are drawn that the contamination sources of these polycyclic aromatic hydrocarbons are likely petrogenic and pyrolytic inputs. Future investigations by sampling topsoil, vadose soil, and the atmosphere can further verify aforementioned conclusions.

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

DTIC Science & Technology

1986-01-01

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

Determination and source identification of priority polycyclic aromatic hydrocarbons in PM2.5 in Taiyuan, China

NASA Astrophysics Data System (ADS)

Zhang, Meng; Xie, Jingfang; Wang, Zhentao; Zhao, Lijuan; Zhang, Hong; Li, Meng

2016-09-01

Sixteen polycyclic aromatic hydrocarbons (PAHs) present in PM2. 5 were analyzed in 2012 in Taiyuan (China) using high performance liquid chromatography (HPLC) with fluorescence and ultraviolet detectors. The average daily mass concentrations of ΣPAHs in different seasons ranged from 10.36 ng/m3 to 215.93 ng/m3 and had strong seasonal variation, with highest values in winter and lowest in summer. Over the whole year, PAHs appeared in the following order of frequency: 4-ring > 6-ring > 5-ring > 3-ring; in winter, the percentage of 4-ring PAHs was the highest (62.68%), while in summer, the percentages of 5-ring and 6-ring PAHs (cumulative total of 50.57%) were higher. The ratio method was employed to investigate potential source categories of PAHs in PM2.5 in Taiyuan, with data suggesting that the main PAH sources are coal and wood combustion and vehicle emissions. Finally, a risk assessment of PAHs was performed based on benzo(a)pyrene equivalent (BaPeq) values and individual cancer risk ratios, with results suggesting that the toxicity of PAHs was high during winter and spring time in Taiyuan. The values of incremental lifetime cancer risk (ILCR) induced by whole year inhalation exposure(Ri) for all age groups were larger than 10- 6 in spring and winter, while Ri values for male and female adults in summer and autumn were also larger than 10- 6, indicating high potential carcinogenic risk. During the same season, the ILCR of adults was greater than that of other age groups and that of females was a little higher than of males. With respect to the season, the ranking of ILCR in decreasing order was as follows: winter, spring, autumn, and summer.

Aliphatic and polycyclic aromatic hydrocarbons in the Xihe River, an urban river in China's Shenyang City: distribution and risk assessment.

PubMed

Guo, Wei; He, Mengchang; Yang, Zhifeng; Lin, Chunye; Quan, Xiangchun

2011-02-28

The characteristics of petroleum hydrocarbons and the risks they pose to the ecosystem were studied in the Xihe River, which is an urban river located in Shenyang, China. High levels of aliphatic hydrocarbons (AHc) and polycyclic aromatic hydrocarbons (PAHs) were observed in the river due to the discharge of wastewater from industrial and municipal facilities for a long period of time. High-molecular-weight hydrocarbons, including unresolved complex mixtures (UCM) of n-alkanes between n-C16 and n-C32 and of PAHs with four to six rings, were the dominant hydrocarbons in the river, particularly in suspended particulate matter (SPM) and sediments. The AHc was mainly from petrogenic sources, whereas PAHs was from both pyrolytic and petrogenic source inputs. Our results suggest that there is a high risk of toxicity for the soils and groundwater of the study area. The overall toxicity in the sediments can be described using the toxic equivalent (TEQ) of dibenzo[a,h]anthracene (DBA) based on benzo(a)pyrene (TEQ(BaP)) and dioxins (TEQ(TCDD)) toxic equivalent concentrations. The TEQ values for benzo(a)pyrene (TEQ(BaP)) and dioxins (TEQ(TCDD)) presented a consistent assessment of sediment PAHs. Crown Copyright © 2010. Published by 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.

Assessment of polycyclic aromatic hydrocarbons (PAHs) pollution in soil of suburban areas in Tianjin, China.

PubMed

Lv, Jungang; Shi, Rongguang; Cai, Yanming; Liu, Yong

2010-07-01

Soil contamination with polycyclic aromatic hydrocarbons is an increasing problem and has aroused more and more concern in many countries, including China. In this study, representative soil samples (n = 87) of suburban areas in Tianjin (Xiqing, Dongli, Jinnan, Beichen) were evaluated for 16 polycyclic aromatic hydrocarbons. Surface soil samples were air-dried and sieved. Microwave assisted extraction was used for polycyclic aromatic hydrocarbons preparation prior to analysis with gas chromatography-mass spectrometry. The total concentrations of tested polycyclic aromatic hydrocarbons in Xiqing, Dongli, Jinnan, Beichen ranged in 58.5-2,748.3, 36.1-6,734.7, 58.5-4,502.5, 29.7-852.5 ng/g and the averages of total concentration of polycyclic aromatic hydrocarbons were 600.5, 933.6, 640.8, 257.3 ng/g, respectively. Spatial variation of polycyclic aromatic hydrocarbons in soil was illustrated; Pollution status and comparison to other cities were also investigated. Serious polycyclic aromatic hydrocarbons soil pollution was found in Dongli district, on the contrary, Bap in most sites in Beichen did not exceed relative standards and most sites in Beichen should be classified as non-contaminated soil. Principal component analysis was used to identify the possible sources of different districts. It turned out that coal combustion still was the most important sources in three districts except Beichen. Coking, traffic, cooking, biomass combustion also accounted for polycyclic aromatic hydrocarbons pollution to certain extent in different districts. These data can be further used to assess the health risk associated with soils polluted with polycyclic aromatic hydrocarbons and help local government find proper way to reduce polycyclic aromatic hydrocarbons pollution in soils.

Structural Mechanism of Replication Stalling on a Bulky Amino-Polycyclic Aromatic Hydrocarbon DNA Adduct by a Y Family DNA Polymerase

PubMed Central

Kirouac, Kevin N.; Basu, Ashis K.; Ling, Hong

2013-01-01

Polycyclic aromatic hydrocarbons and their nitro derivatives are culprits of the detrimental health effects of environmental pollution. These hydrophobic compounds metabolize to reactive species and attach to DNA producing bulky lesions, such as N-[deoxyguanosine-8-yl]-1-aminopyrene (APG), in genomic DNA. The bulky adducts block DNA replication by high-fidelity polymerases and compromise replication fidelities and efficiencies by specialized lesion bypass polymerases. Here we present three crystal structures of the DNA polymerase Dpo4, a model translesion DNA polymerase of the Y family, in complex with APG-lesion-containing DNA in pre-insertion and extension stages. APG is captured in two conformations in the pre-insertion complex; one is highly exposed to the solvent, whereas the other is harbored in a shallow cleft between the finger and unique Y family little finger domain. In contrast, APG is in a single conformation at the extension stage, in which the pyrene ring is sandwiched between the little finger domain and a base from the turning back single-stranded template strand. Strikingly, a nucleotide intercalates the DNA helix to form a quaternary complex with Dpo4, DNA, and an incoming nucleotide, which stabilizes the distorted DNA structure at the extension stage. The unique APG DNA conformations in Dpo4 inhibit DNA translocation through the polymerase active site for APG bypass. We also modeled an insertion complex that illustrates a solvent-exposed pyrene ring contributing to an unstable insertion state. The structural work combined with our lesion replication assays provides a novel structural mechanism on bypass of DNA adducts containing polycyclic aromatic hydrocarbon moieties. PMID:23876706

Structural mechanism of replication stalling on a bulky amino-polycyclic aromatic hydrocarbon DNA adduct by a y family DNA polymerase.

PubMed

Kirouac, Kevin N; Basu, Ashis K; Ling, Hong

2013-11-15

Polycyclic aromatic hydrocarbons and their nitro derivatives are culprits of the detrimental health effects of environmental pollution. These hydrophobic compounds metabolize to reactive species and attach to DNA producing bulky lesions, such as N-[deoxyguanosine-8-yl]-1-aminopyrene (APG), in genomic DNA. The bulky adducts block DNA replication by high-fidelity polymerases and compromise replication fidelities and efficiencies by specialized lesion bypass polymerases. Here we present three crystal structures of the DNA polymerase Dpo4, a model translesion DNA polymerase of the Y family, in complex with APG-lesion-containing DNA in pre-insertion and extension stages. APG is captured in two conformations in the pre-insertion complex; one is highly exposed to the solvent, whereas the other is harbored in a shallow cleft between the finger and unique Y family little finger domain. In contrast, APG is in a single conformation at the extension stage, in which the pyrene ring is sandwiched between the little finger domain and a base from the turning back single-stranded template strand. Strikingly, a nucleotide intercalates the DNA helix to form a quaternary complex with Dpo4, DNA, and an incoming nucleotide, which stabilizes the distorted DNA structure at the extension stage. The unique APG DNA conformations in Dpo4 inhibit DNA translocation through the polymerase active site for APG bypass. We also modeled an insertion complex that illustrates a solvent-exposed pyrene ring contributing to an unstable insertion state. The structural work combined with our lesion replication assays provides a novel structural mechanism on bypass of DNA adducts containing polycyclic aromatic hydrocarbon moieties. © 2013.

Polygonal current models for polycyclic aromatic hydrocarbons and graphene sheets of various shapes.

PubMed

Pelloni, Stefano; Lazzeretti, Paolo

2018-01-05

Assuming that graphene is an "infinite alternant" polycyclic aromatic hydrocarbon resulting from tessellation of a surface by only six-membered carbon rings, planar fragments of various size and shape (hexagon, triangle, rectangle, and rhombus) have been considered to investigate their response to a magnetic field applied perpendicularly. Allowing for simple polygonal current models, the diatropicity of a series of polycyclic textures has been reliably determined by comparing quantitative indicators, the π-electron contribution to I B , the magnetic field-induced current susceptibility of the peripheral circuit, to ξ∥ and to σ∥(CM)=-NICS∥(CM), respectively the out-of-plane components of the magnetizability tensor and of the magnetic shielding tensor at the center of mass. Extended numerical tests and the analysis based on the polygonal model demonstrate that (i) ξ∥ and σ∥(CM) yield inadequate and sometimes erroneous measures of diatropicity, as they are heavily flawed by spurious geometrical factors, (ii) I B values computed by simple polygonal models are valid quantitative indicators of aromaticity on the magnetic criterion, preferable to others presently available, whenever current susceptibility cannot be calculated ab initio as a flux integral, (iii) the hexagonal shape is the most effective to maximize the strength of π-electron currents over the molecular perimeter, (iv) the edge current strength of triangular and rhombic graphene fragments is usually much smaller than that of hexagonal ones, (v) doping by boron and nitrogen nuclei can regulate and even inhibit peripheral ring currents, (vi) only for very large rectangular fragments can substantial current strengths be expected. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Development of a screening tool to prioritize testing for the carcinogenic hazard of residual aromatic extracts and related petroleum streams.

PubMed

Goyak, Katy O; Kung, Ming H; Chen, Min; Aldous, Keith K; Freeman, James J

2016-12-15

Residual aromatic extracts (RAE) are petroleum substances with variable composition predominantly containing aromatic hydrocarbons with carbon numbers greater than C25. Because of the high boiling nature of RAEs, the aromatics present are high molecular weight, with most above the range of carcinogenic polycyclic aromatic hydrocarbons (PAHs). However, refinery distillations are imperfect; some PAHs and their heteroatom-containing analogs (collectively referred to as polycyclic aromatic content or PAC) may remain in the parent stream and be extracted into the RAE, and overall PAC content is related to the carcinogenic potential of an RAE. We describe here a real-time analytical chemistry-based tool to assess the carcinogenic hazard of RAE via the development of a functional relationship between carcinogenicity and boiling point. Samples representative of steps along the RAE manufacturing process were obtained from five refineries to evaluate relationships between mutagenicity index (MI), PAC ring content and gas chromatographic distillation (GCD) curves. As expected, a positive linear relationship between MI and PAC ring content occurred, most specifically for 3-6 ring PAC (R 2 =0.68). A negative correlation was found between MI and temperature at 5% vaporization by GCD (R 2 =0.72), indicating that samples with greater amounts of lower boiling constituents were more likely to be carcinogenic. The inverse relationship between boiling range and carcinogenicity was further demonstrated by fractionation of select RAE samples (MI=0.50+0.07; PAC=1.70+0.51wt%; n=5) into low and high boiling fractions, where lower boiling fractions were both more carcinogenic than the higher boiling fractions (MI=2.36±0.55 and 0.17±0.11, respectively) and enriched in 3-6 ring PACs (5.20+0.70wt% and 0.97+0.35wt%, respectively). The criteria defining carcinogenicity was established as 479°C for the 5% vaporization points by GCD, with an approximate 95% probability of a future sample having an MI below the recommended limit of 0.4 for RAEs. Overall, these results provide a cost-efficient and real-time tool by which the carcinogenic potential of RAEs can be assessed at the refinery level, ultimately providing a means to readily monitor and minimize the carcinogenic potential of RAEs. Copyright © 2016. Published by Elsevier Ireland Ltd.

Effect of water flux and sediment discharge of the Yangtze River on PAHs sedimentation in the estuary.

PubMed

Li, Rufeng; Feng, Chenghong; Wang, Dongxin; He, Maozhi; Hu, Lijuan; Shen, Zhenyao

2016-12-01

Historical distribution characteristics of polycyclic aromatic hydrocarbons (PAHs) and their carriers (i.e., organic matter and mineral particles) in the sediment cores of the Yangtze Estuary were investigated, with emphasis laid on the role of the Yangtze River. Grain size component of sediments (clay, silt, and sand) and organic carbon (black carbon and total organic carbon) in the sediment cores were markedly affected by water flux and sediment discharge of the Yangtze River. Qualitative and quantitative analysis results showed that sands and black carbon acted as the main carriers of PAHs. The sedimentation of two-ring to three-ring PAHs in the estuary had significant correlations with water flux and sediment discharge of the Yangtze River. The relative lower level of the four-ring and five-ring to six-ring PAHs concentrations appeared around the year 2003 and remained for the following several years. This time period accorded well with the water impoundment time of the Three Gorges Reservoir. The decreased level of two-ring to three-ring PAHs occurred in the year 1994, and the peak points around the year 2009 indicated that PAHs sedimentation in the estuary also had close relationship to severe drought and flood in the catchments. The findings presented in this paper could provide references for assessing the impacts of water flux and sediment discharge on the historical deposition of PAHs and their carriers in the Yangtze Estuary.

Suspended particulate matter collection methods influence the quantification of polycyclic aromatic compounds in the river system.

PubMed

Abuhelou, Fayez; Mansuy-Huault, Laurence; Lorgeoux, Catherine; Catteloin, Delphine; Collin, Valéry; Bauer, Allan; Kanbar, Hussein Jaafar; Gley, Renaud; Manceau, Luc; Thomas, Fabien; Montargès-Pelletier, Emmanuelle

2017-10-01

In this study, we compared the influence of two different collection methods, filtration (FT) and continuous flow field centrifugation (CFC), on the concentration and the distribution of polycyclic aromatic compounds (PACs) in suspended particulate matter (SPM) occurring in river waters. SPM samples were collected simultaneously with FT and CFC from a river during six sampling campaigns over 2 years, covering different hydrological contexts. SPM samples were analyzed to determine the concentration of PACs including 16 polycyclic aromatic hydrocarbons (PAHs), 11 oxygenated PACs (O-PACs), and 5 nitrogen PACs (N-PACs). Results showed significant differences between the two separation methods. In half of the sampling campaigns, PAC concentrations differed from a factor 2 to 30 comparing FT and CFC-collected SPMs. The PAC distributions were also affected by the separation method. FT-collected SPM were enriched in 2-3 ring PACs whereas CFC-collected SPM had PAC distributions dominated by medium to high molecular weight compounds typical of combustion processes. This could be explained by distinct cut-off threshold of the two separation methods and strongly suggested the retention of colloidal and/or fine matter on glass-fiber filters particularly enriched in low molecular PACs. These differences between FT and CFC were not systematic but rather enhanced by high water flow rates.

Ancient water bottle use and polycyclic aromatic hydrocarbon (PAH) exposure among California Indians: a prehistoric health risk assessment.

PubMed

Sholts, Sabrina B; Smith, Kevin; Wallin, Cecilia; Ahmed, Trifa M; Wärmländer, Sebastian K T S

2017-06-23

Polycyclic aromatic hydrocarbons (PAHs) are the main toxic compounds in natural bitumen, a fossil material used by modern and ancient societies around the world. The adverse health effects of PAHs on modern humans are well established, but their health impacts on past populations are unclear. It has previously been suggested that a prehistoric health decline among the native people living on the California Channel Islands may have been related to PAH exposure. Here, we assess the potential health risks of PAH exposure from the use and manufacture of bitumen-coated water bottles by ancient California Indian societies. We replicated prehistoric bitumen-coated water bottles with traditional materials and techniques of California Indians, based on ethnographic and archaeological evidence. In order to estimate PAH exposure related to water bottle manufacture and use, we conducted controlled experiments to measure PAH contamination 1) in air during the manufacturing process and 2) in water and olive oil stored in a completed bottle for varying periods of time. Samples were analyzed with gas chromatography/mass spectrometry (GC/MS) for concentrations of the 16 PAHs identified by the US Environmental Protection Agency (EPA) as priority pollutants. Eight PAHs were detected in concentrations of 1-10 μg/m 3 in air during bottle production and 50-900 ng/L in water after 2 months of storage, ranging from two-ring (naphthalene and methylnaphthalene) to four-ring (fluoranthene) molecules. All 16 PAHs analyzed were detected in olive oil after 2 days (2 to 35 μg/kg), 2 weeks (3 to 66 μg/kg), and 2 months (5 to 140 μg/kg) of storage. For ancient California Indians, water stored in bitumen-coated water bottles was not a significant source of PAH exposure, but production of such bottles could have resulted in harmful airborne PAH exposure.

[Experimental study on the characteristics polycyclic aromatic hydrocarbon emissions of diesel engine burnt by different fuels].

PubMed

Wang, Zhong; An, Yu-Guang; Xu, Guang-Ju; Wang, Xiao-Zhe

2011-07-01

The polycyclic aromatic hydrocarbons (PAHs) were measured by glass fiber filter and XAD-2 collector, ultrasonic extraction, soxhlet extraction and GC-MS analysis equipment. The exhaust emission of the DI single cylinder diesel engine fueled with pure diesel, biodiesel and biodiesel blends of 50% (B50) were measured. The results indicate that the particle-phase PAHs emissions of diesel engine decrease with the increasing of load. The gas-phase PAHs emissions of diesel engine decrease with the increasing of load in the beginning and it turns to going up with further increasing of load. The particle-phase and gas-phase PAHs emissions of biodiesel decrease and mean concentration are lower than that of diesel. The total PAHs emission concentration of biodisesl is 41.1-70.1 microg/m3. Total PAHs mean concentration emissions of biodiesel is decreased 33.3% than that of diesel. The mass proportion of three-ring PAHs emissions of those 3 kinds tested fuels is about 44% in the total PAHs. Biodiesel can increase the proportion of three-ring PAHs. Toxic equivalence of PAHs emissions of biodiesel are greatly lower than that of diesel. It is less harmful to human than diesel fuel.

Determination of polycyclic aromatic hydrocarbons in urine of coke oven workers by headspace solid phase microextraction and gas chromatography-mass spectrometry.

PubMed

Waidyanatha, Suramya; Zheng, Yuxin; Rappaport, Stephen M

2003-05-06

Polycyclic aromatic hydrocarbons (PAHs) represent a complex mixture of toxic compounds that are ubiquitous in the environment. We investigated the utility of head space-solid phase microextraction (HS-SPME) to measure the following surrogate PAHs in urine: naphthalene (NAP), phenanthrene (PHE), pyrene (PYR), and benzo(a)pyrene (BAP), representing classes of 2-, 3-, 4- and 5-ring compounds, respectively. We then applied the method to urine from 28 coke oven workers (median levels (microg/l) were: NAP=3.65, PHE=1.51, PYR=0.003, BAP not detected) and 22 controls (median (microg/l) NAP=0.859, PHE=0.062, PYR=0.001, BAP not detected). Urinary levels of NAP, PHE, and PYR were all associated with exposure category (controls, side- and bottom-workers, and top-workers) but not with smoking status. Strong correlations were observed between urinary levels of NAP, PHE, and PYR in coke-oven workers. Our results indicate that unmetabolized 2-, 3- and 4-ring PAHs can be measured in urine by HS-SPME. Such measurements can be used to investigate the uptake and metabolism of complex PAH mixtures in humans.

POLYCYCLIC AROMATIC HYDROCARBONS ASSESSMENT IN SEDIMENT OF NATIONAL PARKS IN SOUTHEAST BRAZIL

PubMed Central

Meire, Rodrigo Ornellas; Azeredo, Antonio; de Souza Pereira, Márcia; Paulo, João; Torres, Machado; Malm, Olaf

2008-01-01

The aim of this work was to assess the levels of polycyclic aromatic hydrocarbons (PAHs) in the environment and their sources found in protected regions of southeastern Brazil. Samples of sediments were collected at four National Parks: Itatiaia National Park (PNIT), Serra da Bocaina National Park (PNSB), Serra dos Orgãos National Park (PNSO) and Jurubatiba National Park (PNJUB). The National Parks studied comprise rainforests, altitudinal fields and ‘restinga’ environments located in the Minas Gerais, Rio de Janeiro and São Paulo states. The sampling was conducted between 2002 and 2004 from June to September. In general, the environmental levels of PAHs found were similar to those in other remote areas around the globe. PNIT exhibited the highest median values of total PAHs in sediment (97 ng·g−1), followed by PNJUB (89 ng·g−1), PNSO (57 ng·g−1) and PNSB (27 ng·g−1). The highest levels of total PAHs (576 and 24430 ng·g−1) could be associated to a point source contamination where are characterizated for human activities. At PNSB and PNIT the PAH profiles were richer in 2 and 3 ring compounds, whereas at PNSO and PNJUB, the profiles exhibited 3 and 4 ring compounds. The phenanthrene predominance in most samples could indicate the influence of biogenic synthesis. The samples with a petrogenic pattern found in this study might be associated with the vicinity of major urban areas, highway traffic and/or industrial activities close to PNSO and PNIT. At PNIT and PNJUB, forest fires and slash and burn agricultural practices may drive the results towards a pyrolytic pattern. PMID:18472130

Responses of metabolic pathways to polycyclic aromatic compounds in flounder following oil spill in the Baltic Sea near the Estonian coast.

PubMed

Kreitsberg, Randel; Zemit, Irina; Freiberg, Rene; Tambets, Meelis; Tuvikene, Arvo

2010-09-15

In January 2006 an oil spill that involved approximately 40tons of heavy fuel oil affected more than 30km of the north-west coast of Estonia. The aquatic pollution of the coastal area of the Baltic Sea was monitored by measuring the content of selected polycyclic aromatic hydrocarbons (PAHs and PAH metabolites) in flounder (Platichthys flesus trachurus Duncker). One hundred and thirty-one fish were collected: muscle and liver tissues were analyzed by high-performance liquid chromatography (HPLC); bile and urine samples were analyzed using fixed wavelengths fluorescence. Fifteen different types of PAHs were analyzed in liver and muscle, and four types of PAH metabolites were analyzed in bile and urine (2-, 3-, 4- and 5-ringed PAH metabolites represented by naphthalene, phenanthrene, pyrene and benzo(a)pyrene). Fluorescence analyses were carried out using excitation/emission wavelength pairs: 290/380, 256/380, 341/383 and 380/430nm, respectively. There was a time-dependent decrease of PAH concentrations in liver (83%), bile (82%) and urine (113%). HPLC analysis of muscle tissues demonstrated low concentrations of single PAHs, but a decrease of concentrations during the study period was not observed. During the analyses concentrations of PAH metabolites in bile and urine were compared. Liver metabolic transformation activity is believed to exceed that of the kidney but the analyses demonstrated high metabolite concentration in fish urine, particularly of 4- and 5-ring PAH metabolites. The results indicate remarkable buffer capacity of hydrodynamically active sea as well as considerable importance of kidney-urine metabolic pathways in flounder physiology. 2010 Elsevier B.V. All rights reserved.

Polycyclic aromatic hydrocarbons (PAHs) concentration levels, pattern, source identification and soil toxicity assessment in urban traffic soil of Dhanbad, India.

PubMed

Suman, Swapnil; Sinha, Alok; Tarafdar, Abhrajyoti

2016-03-01

Present study was carried out to assess and understand potential health risk and to examine the impact of vehicular traffic on the contamination status of urban traffic soils in Dhanbad City with respect to polycyclic aromatic hydrocarbons (PAHs). Eight urban traffic sites and two control/rural site surface soils were analyzed and the contents of 13 priority PAHs was determined. Total PAH concentration at traffic sites ranged from 1.019 μg g(-1) to 10.856 μg g(-1) with an average value of 3.488 μg g(-1). At control/rural site, average concentration of total PAHs was found to be 0.640 μg g(-1). PAH pattern was dominated by four- and five-ring PAHs (contributing >50% to the total PAHs) at all the eight traffic sites. On the other hand, rural soil showed a predominance of low molecular weight three-ring PAHs (contributing >30% to the total PAHs). Indeno[123-cd]pyrene/benz[ghi]perylene (IP/BgP) ratio indicated that PAH load at the traffic sites is predominated by the gasoline-driven vehicles. The ratio of Ant/(Ant+Phe) varied from 0.03 to 0.44, averaging 0.10; Fla/(Fla+Pyr) from 0.39 to 0.954, averaging 0.52; BaA/(BaA+Chry) from 0.156 to 0.60, averaging 0.44; and IP/(IP+BgP) from 0.176 to 0.811, averaging 0.286. The results indicated that vehicular emission was the major source for PAHs contamination with moderate effect of coal combustion and biomass combustion. Carcinogenic potency of PAH load in traffic soil was nearly 6.15 times higher as compared to the control/rural soil. Copyright © 2015 Elsevier B.V. All rights reserved.

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

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.

Polycyclic aromatic hydrocarbons (PAHs) in atmospheric dustfall from the industrial corridor in Hubei Province, Central China.

PubMed

Zhang, Jiaquan; Qu, Chengkai; Qi, Shihua; Cao, Junji; Zhan, Changlin; Xing, Xinli; Xiao, Yulun; Zheng, Jingru; Xiao, Wensheng

2015-10-01

Thirty atmospheric dustfall samples collected from an industrial corridor in Hubei Province, central China, were analyzed for 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) to investigate their concentrations, spatial distributions, sources, and health risks. Total PAH concentrations (ΣPAHs) ranged from 1.72 to 13.17 µg/g and averaged 4.91 µg/g. High molecular weight (4-5 rings) PAHs averaged 59.67% of the ΣPAHs. Individual PAH concentrations were not significantly correlated with total organic carbon, possibly due to the semi-continuous inputs from anthropogenic sources. Source identification studies suggest that the PAHs were mainly from motor vehicles and biomass/coal combustion. The incremental lifetime cancer risks associated with exposure to PAHs in the dustfall ranged from 10(-4) to 10(-6); these indicate potentially serious carcinogenic risks for exposed populations in the industrial corridor.

Polycyclic aromatic hydrocarbons (PAHs) in wild marine organisms from South China Sea: Occurrence, sources, and human health implications.

PubMed

Ke, Chang-Liang; Gu, Yang-Guang; Liu, Qi; Li, Liu-Dong; Huang, Hong-Hui; Cai, Nan; Sun, Zhi-Wei

2017-04-15

Concentrations of 16 US EPA priority polycyclic aromatic hydrocarbons (PAHs) were measured in 15 marine wild organism species from South China Sea. The concentration (dry weight) of 16 PAHs ranged from 94.88 to 557.87ng/g, with a mean of 289.86ng/g. The concentrations of BaP in marine species were no detectable. The composition of PAHs was characterized by the 2- and 3-ring PAHs in marine species, and NA, PHE and FA were the dominant constituents. PAHs isomeric ratios indicated PAHs mainly originated from grass, wood and coal combustion, and petroleum. The human health risk assessment based on the excess cancer risk (ECR) suggested the probability of PAHs posing carcinogenic risk to human beings with consumption of marine organisms were negligible (probability<1×10 -6 ). Copyright © 2017 Elsevier Ltd. All rights reserved.

Rational engineering of the fungal P450 monooxygenase CYP5136A3 to improve its oxidizing activity toward polycyclic aromatic hydrocarbons.

PubMed

Syed, Khajamohiddin; Porollo, Aleksey; Miller, David; Yadav, Jagjit S

2013-09-01

A promising polycyclic aromatic hydrocarbon-oxidizing P450 CYP5136A3 from Phanerochaete chrysosporium was rationally engineered to enhance its catalytic activity. The residues W129 and L324 found to be critical in substrate recognition were transformed by single (L324F) and double (W129L/L324G, W129L/L324F, W129A/L324G, W129F/L324G and W129F/L324F) mutations, and the engineered enzyme forms were expressed in Pichia pastoris. L324F and W129F/L324F mutations enhanced the oxidation activity toward pyrene and phenanthrene. L324F also altered the regio-selectivity favoring C position 4 over 9 for hydroxylation of phenanthrene. This is the first instance of engineering a eukaryotic P450 for enhanced oxidation of these fused-ring hydrocarbons.

Characterization of polycyclic aromatic hydrocarbons and carbonyl compounds in diesel exhaust emissions.

PubMed

Mabilia, Rosanna; Cecinato, Angelo; Tomasi Scianò, Maria Concetta; Di Palo, Vincenzo; Possanzini, Massimiliano

2004-01-01

Exhaust emissions from a recent model heavy-duty diesel vehicle (city bus) in a chassis dynamometer were measured during a transient driving cycle. Particle-bound polycyclic aromatic hydrocarbons (PAHs) and gaseous carbonyls, substances that create health hazards and are, as yet, unregulated were collected, the former on filters and the latter on dinitrophenylhydrazine (DNPH)-coated silica cartridges and analysed by GC-MS and HPLC, respectively. PAH emission rates decreased with the number of benzene fused rings. They averaged 0.2 mg km(-1) for a total of 11 PAHs ranging from fluoranthene to benzo(ghi)perylene. Fluoranthene and pyrene accounted for 90% of total PAHs. The sum of emission rates of C1 approximately C6 carbonyls averaged 174 mg km(-1), even if formaldehyde alone represented approximately 70% of the total carbonyl mass, followed by acetaldehyde (13%). Results obtained were compared with emission data reported in previous studies.

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

NASA Astrophysics Data System (ADS)

Zhidkin, Andrey; Koshovskii, Timur; Gennadiev, Alexander

2016-04-01

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

Laboratory rotational spectroscopy of cyano substituted polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

McNaughton, Don; Jahn, Michaela K.; Travers, Michael J.; Wachsmuth, Dennis; Godfrey, Peter D.; Grabow, Jens-Uwe

2018-06-01

The rotational spectra of the four cyano substituted polycyclic aromatic hydrocarbon (PAH) molecules 1-cyanonaphthalene, 2-cyanonaphthalene, 9-cyanoanthracene, and 9-cyanophenanthrene have been recorded in molecular expansions using a Stark-modulated millimetre-wave spectrometer and a Fourier transform microwave spectrometer in the centimetre-wave region. The spectra have been assigned and fitted to provide molecular constants and quadrupole hyperfine constants of sufficient accuracy to enable complete hyperfine structure line predictions for interstellar searches. The data may provide a route into detection of small PAHs in the interstellar medium.

Interactive effects of PAHs with different rings and As on their uptake, transportation, and localization in As hyperaccumulator.

PubMed

Liao, Xiaoyong; Wu, Zeying; Ma, Xu; Gong, Xuegang; Yan, Xiulan

2017-11-01

In order to illuminate the mechanism of the interaction of polycyclic aromatic hydrocarbon (PAH) with different benzene rings and arsenic (As) in As hyperaccumulator, Pteris vittata L., the uptakes of PAHs were investigated using hydroponics simulation and localizations of PAHs in the plant were determined using two-photon laser scanning confocal microscopy (TPLSCM). The results showed that the total As concentration in different parts of P. vittata decreased in the presence of PAHs with increased numbers of benzene rings: 38.0-47.4% for benzo(a)pyrene (BaP, five rings), 20.5-35.9% for pyrene (PYR, four rings), and 13.7-16.6% for fluorine (FLU, three rings). BaP and PYR concentrations increased, while FLU concentration decreased in the presence of As. The results of TPLSCM revealed that PAHs distributed in epidermal cells of roots, xylem, and endothelial cells of rachis, epidermis, and stomatal cells of pinnae; however, the fluorescence intensity of BaP and PYR were higher than FLU significantly in plant. This study provided important basis to further research on interactive effects of PAHs and As in the P. vittata. These findings were important to understand the mechanisms of PAH and As translocation and distribution by P. vittata.

Attributing risk burden of PM2.5-bound polycyclic aromatic hydrocarbons to major emission sources: Case study in Guangzhou, south China

NASA Astrophysics Data System (ADS)

Yu, Qingqing; Gao, Bo; Li, Guanghui; Zhang, Yanli; He, Quanfu; Deng, Wei; Huang, Zhonghui; Ding, Xiang; Hu, Qihou; Huang, Zuzhao; Wang, Yujun; Bi, Xinhui; Wang, Xinming

2016-10-01

Polycyclic aromatic hydrocarbons (PAHs) have attracted an increasing concern in China's megacities. However, rare information is available on the spatial and seasonal variations of inhalation cancer risk (ICR) due to PAH exposure and their relations to specific sources. In this study, year-round PM2.5 samples were collected from 2013 to 2014 by high-volume samplers at four sites (one urban, two rural and one roadside station) in Guangzhou in the highly industrialized and densely populated Pearl River Delta (PRD) region and analyzed for 26 polycyclic aromatic hydrocarbons (PAHs) together with molecular tracers including levoglucosan, hopanes and elemental carbon. Higher molecular weight PAHs (5-ring or above) accounted for 64.3-87.5% of total PAHs. Estimated annual averages of benzo(a)pyrene-equivalent carcinogenic potency (BaPeq) were 1.37, 2.31 and 1.56 ng/m3 at urban SZ, rural JL and rural WQS, respectively, much higher than that at the roadside station YJ in an urban street canyon. ICR of PAHs in wintertime reached 2.2 × 10-4, nearly 3 times that in summer; and cancer risk of PAHs was surprisingly higher at the rural site than at other sites. Source contributions by positive matrix factorization (PMF) in the aid of molecular tracers revealed that overall coal combustion and biomass burning altogether contributed 73.8% of total PAHs and 85.2% of BaPeq, and particularly in winter biomass burning became the most significant source of total PAHs and BaPeq (51.8% and 52.5%), followed by coal combustion (32.0% and 39.1%) and vehicle emission (16.2% and 8.4%). The findings of this work suggest that even in China's megacities like Guangzhou, limiting biomass burning may benefit PAHs pollution control and cancer risk reduction.

Emissions of particulate matter and associated polycyclic aromatic hydrocarbons from agricultural diesel engine fueled with degummed, deacidified mixed crude palm oil blends.

PubMed

Phoungthong, Khamphe; Tekasakul, Surajit; Tekasakul, Perapong; Prateepchaikul, Gumpon; Jindapetch, Naret; Furuuchi, Masami; Hata, Mitsuhiko

2013-04-01

Mixed crude palm oil (MCPO), the mixture of palm fiber oil and palm kernel oil, has become of great interest as a renewable energy source. It can be easily extracted from whole dried palm fruits. In the present work, the degummed, deacidified MCPO was blended in petroleum diesel at portions of 30% and 40% by volume and then tested in agricultural diesel engines for long-term usage. The particulates from the exhaust of the engines were collected every 500 hr using a four-stage cascade air sampler. The 50% cut-off aerodynamic diameters for the first three stages were 10, 2.5 and 1 microm, while the last stage collected all particles smaller than 1 microm. Sixteen particle bounded polycyclic aromatic hydrocarbons (PAHs) were analyzed using a high performance liquid chromatography. The results indicated that the size distribution of particulate matter was in the accumulation mode and the pattern of total PAHs associated with fine-particles (< 1 microm) showed a dominance of larger molecular weight PAHs (4-6 aromatic rings), especially pyrene. The mass median diameter, PM and total PAH concentrations decreased when increasing the palm oil content, but increased when the running hours of the engine were increased. In addition, Commercial petroleum diesel (PB0) gave the highest value of carcinogenic potency equivalent (BaP(eq)) for all particle size ranges. As the palm oil was increased, the BaP(eq) decreased gradually. Therefore the degummed-deacidified MCPO blends are recommended for diesel substitute.

Boron nitride nanotubes as novel sorbent for solid-phase microextraction of polycyclic aromatic hydrocarbons in environmental water samples.

PubMed

Fu, Meizhen; Xing, Hanzhu; Chen, Xiangfeng; Zhao, Rusong; Zhi, Chunyi; Wu, Chiman Lawrence

2014-09-01

Boron nitride nanotube (BNNT) is a novel material that shows potential ability in capturing organic pollutants. In this study, BNNTs fixed on a stainless steel fiber by a sol-gel technique were used as sorbent for solid-phase microextraction. Five polycyclic aromatic hydrocarbons with different numbers of aromatic rings were selected as target analysts. Gas chromatography coupled with tandem mass spectrometry was used for detection and quantitative determination. Under optimized conditions, the experimental results show a wide range of linearity (1 to 1,000 ng L(-1)), less than 10.1 % repeatability of relative standard deviation, and low detection limits (0.08 to 0.39 ng L(-1)). In addition, the fabricated fiber offered good thermal and chemical stability. The proposed method was successfully applied for the analysis of real water samples, and satisfactory results were obtained with relative recoveries ranging from 80.2 to 116.8 %. The results demonstrated that BNNTs could be used as sorbent for the analysis of environmental pollutants at trace levels.

Interstellar Polycyclic Aromatic Compounds and Astrophysics

NASA Technical Reports Server (NTRS)

Hodgins, Douglas M.; DeVincenzi, Donald (Technical Monitor)

1999-01-01

Polycyclic aromatic compounds (PACs), a class of organic molecules whose structures are characterized by the presence of two or more fused aromatic rings, have been the subject of astrophysical interest for nearly two decades. Large by interstellar standards (from as few as 20 to perhaps as many as several hundred atoms), it has been suggested that these species are among the most abundant interstellar molecules impacting a wide range of astrophysical phenomena including: the ubiquitous family of infrared emission bands observed in an ever-increasing assortment of astronomical objects; the subtle but rich array of discrete visible/near-infrared interstellar molecular absorption features known as the diffuse interstellar bands (DIBs); the broad near-infrared quasi-continuum observed in a number of nebulae known as excess red emission (ERE); the interstellar ultraviolet extinction curve and broad '2200 Angstrom bump'; the heating/cooling mechanisms of interstellar clouds. Nevertheless, until recently a lack of good-quality laboratory spectroscopic data on PACs under astrophysically relevant conditions (i.e. isolated, ionized molecules; ionized molecular clusters, etc.) has hindered critical evaluation and extension of this model

THE PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

The U.S. Environmental Protection Agency (EPA) continues to be interested in developing methods for the detection of polycyclic aromatic hydrocarbons (PAHS) in the environment. Polycyclic aromatic hydrocarbons (PAHS) are common contaminants in our environment. Being major product...

Sediment record of polycyclic aromatic hydrocarbons in the Liaohe River Delta wetland, Northeast China: Implications for regional population migration and economic development.

PubMed

Ma, Chuanliang; Lin, Tian; Ye, Siyuan; Ding, Xigui; Li, Yuanyuan; Guo, Zhigang

2017-03-01

The polycyclic aromatic hydrocarbons (PAHs) of a 210 Pb-dated sediment core extracted from the Liaohe River Delta wetland were measured to reconstruct the sediment record of PAHs and its response to human activity for the past 300 years in Northeast China. The concentrations of the 16 U.S. Environmental Protection Agency priority PAHs (∑16PAHs) ranged from 46 to 1167 ng g -1 in this sediment core. The concentrations of the 16 PAHs (especially 4- and 5+6-ring PAHs) after the 1980s (surface sediments 0-6 cm) were one or two orders of magnitudes higher than those of the down-core samples. The exponential growth of 4-ring and 5+6-ring PAH concentrations after the 1980s responded well to the increased energy consumption and number of civil vehicles resulting from the rapid economic development in China. Prior to 1950, relatively low levels of the 16 PAHs and a high proportion of 2+3-ring PAHs was indicative of biomass burning as the main source of the PAHs. A significant increase in the 2 + 3 ring PAH concentration from the 1860s-1920s was observed and could be attributed to a constant influx of population migration into Northeast China. It was suggested that the link between historical trend of PAHs and population or energy use involves two different economic stages. Typically, in an agricultural economy, the greater the population size, the greater the emission of PAHs from biomass burning, while in an industrial economy, the increase in sedimentary PAH concentrations is closely related to increasing energy consumption of fossil fuels. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polycyclic aromatic hydrocarbons (PAHs) in wetland soils under different land uses in a coastal estuary: toxic levels, sources and relationships with soil organic matter and water-stable aggregates.

PubMed

Xiao, Rong; Bai, Junhong; Wang, Junjing; Lu, Qiongqiong; Zhao, Qingqing; Cui, Baoshan; Liu, Xinhui

2014-09-01

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the soils from industrial, wharf, cropland, milldam and natural wetland sites to characterize their distributions, toxic levels and possible sources in the Pearl River Estuary and identify their relationships with soil organic matter (SOM) and water-stable aggregates (WSAs). Our results indicate that the average concentration of total PAHs in this region reached a moderate pollution level, which was higher than that in other larger estuaries in Asia. The average level of total PAHs in industrial soils was 1.2, 1.5, 1.6 and 2.3 times higher than those in soils from wharf, cropland, milldam and natural wetland sites, respectively. Greater accumulation of PAHs occurred in the middle and/or bottom soil layers where 3-ring PAHs were dominant. Industrial soils also exhibited the highest toxic levels with the highest toxic equivalent concentrations of PAHs, followed by wharf and milldam soils, and the cropland and wetland soils had the lowest toxicity. The diagnostic ratios suggested that PAHs primarily originated from biomass and coal combustion at industrial and milldam sites, and petroleum combustion was determined to be the primary source of PAHs at the wharf, cropland and wetland sites. Both 3-ring and 4-ring PAHs in the milldam and wharf soils were significantly positively correlated with the SOM, whereas the 4,5,6-ring PAHs and total PAHs in industrial soils and the 2-ring PAHs in cropland soils were significantly negatively correlated with the SOM. In addition, large WSAs also exhibited a significant positive correlation with PAHs. Copyright © 2014 Elsevier Ltd. All rights reserved.

π-Extended Star-Shaped Polycyclic Aromatic Hydrocarbons based on Fused Truxenes: Synthesis, Self-Assembly, and Facilely Tunable Emission Properties.

PubMed

Cheng, Cheng; Jiang, Yi; Liu, Cheng-Fang; Zhang, Jian-Dong; Lai, Wen-Yong; Huang, Wei

2016-12-19

A new set of star-shaped polycyclic aromatic hydrocarbons (PAHs) based on naphthalene-fused truxenes, TrNaCn (n=1-4), were synthesized and characterized. The synthesis involved a microwave-assisted six-fold Suzuki coupling reaction, followed by oxidative cyclodehydrogenation. Multiple dehydrocyclization products could be effectively isolated in a single reaction, thus suggesting that the oxidative cyclodehydrogenation reaction involved a stepwise ring-closing process. The thermal, optical, and electrochemical properties and the self-assembly behavior of the resulting oxidized samples were investigated to understand the impact of the ring-fusing process on the properties of the star-shaped PAHs. Distinct bathochromic shift of the absorption maxima (λ max ) revealed that the molecular conjugation extended with the stepwise ring-closing reactions. The optical band-gap energy of these PAHs varied significantly on increasing the number of fused rings, thereby resulting in readily tunable emissive properties of the resultant star-shaped PAHs. Interestingly, the generation of rigid "arms" by using perylene analogues caused TrNaC2 and TrNaC3 to show significantly enhanced photoluminescence quantum yields (PLQYs) in solution (η=0.65 and 0.66, respectively) in comparison with those of TrNa and TrNaC1 (η=0.08 and 0.16, respectively). Owing to strong intermolecular interactions, the TrNa precursor was able to self-assemble into rod-like microcrystals, which could be facilely identified by the naked eye, whilst TrNaC1 self-assembled into nanosheets once the naphthalene rings had fused. This study offers a unique platform to gain further insight into-and a better understanding of-the photophysical and self-assembly properties of π-extended star-shaped PAHs. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coke industry and steel metallurgy as the source of soil contamination by technogenic magnetic particles, heavy metals and polycyclic aromatic hydrocarbons.

PubMed

Rachwał, Marzena; Magiera, Tadeusz; Wawer, Małgorzata

2015-11-01

Application of integrated magnetic, geochemical and mineralogical methods for qualitative and quantitative assessment of forest topsoils exposed to the industrial emissions was the objective of this manuscript. Volume magnetic susceptibility (κ) in three areas of southern Poland close to the coke and metallurgical plants was measured directly in the field. Representative topsoil samples were collected for further chemical and mineralogical analyses. Topsoil magnetic susceptibility in the studied areas depended mainly on the content of technogenic magnetic particles (TMPs) and decreased downwind at increasing distance from the emitters. In the vicinity of coking plants a high amount of polycyclic aromatic hydrocarbons (PAHs) was observed, especially the most carcinogenic ones with four- and five-member rings. No significant concentration of TMPs (estimated on the base of κ values) and heavy metals (HM) was observed in area where the coke plant was the only pollution source. In areas with both coke and metallurgical industry, higher amounts of TMPs, PAHs and HM were detected. Morphological and mineralogical analyses of TMPs separated from contaminated soil samples revealed their high heterogeneity in respect of morphology, grain size, mineral and chemical constitution. Pollution load index and toxicity equivalent concentration of PAHs used for soil quality assessment indicated its high level of pollution. Copyright © 2014 Elsevier Ltd. All rights reserved.

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.

Levels and patterns of polycyclic aromatic hydrocarbons (PAHs) in soils after forest fires in South Korea.

PubMed

Kim, Eun Jung; Choi, Sung-Deuk; Chang, Yoon-Seok

2011-11-01

To investigate the influence of biomass burning on the levels of polycyclic aromatic hydrocarbons (PAHs) in soils, temporal trends and profiles of 16 US Environmental Protection Agency priority PAHs were studied in soil and ash samples collected 1, 5, and 9 months after forest fires in South Korea. The levels of PAHs in the burnt soils 1 month after the forest fires (mean, 1,200 ng/g dry weight) were comparable with those of contaminated urban soils. However, 5 and 9 months after the forest fires, these levels decreased considerably to those of general forest soils (206 and 302 ng/g, respectively). The burnt soils and ash were characterized by higher levels of light PAHs with two to four rings, reflecting direct emissions from biomass burning. Five and 9 months after the forest fires, the presence of naphthalene decreased considerably, which indicates that light PAHs were rapidly volatilized or degraded from the burnt soils. The temporal trend and pattern of PAHs clearly suggests that soils in the forest-fire region can be contaminated by PAHs directly emitted from biomass burning. However, the fire-affected soils can return to the pre-fire conditions over time through the washout and wind dissipation of the ash with high content of PAHs as well as vaporization or degradation of light PAHs.

Synthesis and Structural Data of Tetrabenzo[8]circulene

PubMed Central

Miller, Robert W.; Duncan, Alexandra K.; Schneebeli, Severin T.; Gray, Danielle L.; Whalley, Adam C.

2015-01-01

In 1976, the first attempted synthesis of the saddle-shaped molecule [8]circulene was reported. The next 37 years produced no advancement towards the construction of this complicated molecule. Remarkably, however, over the last six months a flurry of progress has been made with two groups reporting independent and strikingly different strategies for the synthesis of [8]circulene derivatives. Herein, we present a third synthetic method in which we target tetrabenzo[8]circulene. Our approach employs a Diels-Alder reaction and a palladium-catalyzed arylation reaction as the key steps. Despite calculations describing the instability of [8]circulene, coupled with the reported instability of synthesized derivatives of the parent molecule, the addition of four fused benzenoid rings around the periphery of the molecule provides a highly stable structure. This increased stability over the parent [8]circulene was predicted using Clar’s theory of aromatic sextets and is a result of the compound becoming fully benzenoid upon incorporation of these additional rings. The synthesized compound exhibits remarkable stability under ambient conditions – even at elevated temperatures – with no signs of decomposition over several months. The solid-state structure of this compound is significantly twisted compared to the calculated structure primarily as a result of crystal packing forces in the solid state. Despite this contortion from the lowest energy structure, a range of structural data is presented confirming the presence of localized aromaticity in this large polycyclic aromatic hydrocarbon. PMID:24615957

Infrared spectroscopy of hydrated polycyclic aromatic hydrocarbon cations: naphthalene+-water.

PubMed

Chatterjee, Kuntal; Dopfer, Otto

2017-12-13

Polycyclic aromatic hydrocarbons (PAHs) are suggested to occur in interstellar media and ice grains. It is important to characterize hydrated PAHs and their cations to explore their stability in interstellar and biological media. Herein, the infrared photodissociation (IRPD) spectrum of the naphthalene + -H 2 O radical cation (Np + -H 2 O) recorded in the O-H and C-H stretch range is analysed by dispersion-corrected density functional theory calculations at the B3LYP-D3/aug-cc-pVTZ level to determine its structure and intermolecular bonding. Monohydration of Np + in its 2 A u ground electronic state leads to the formation of a bifurcated CHO ionic hydrogen bond (H-bond), in which the lone pairs of H 2 O bind to two adjacent CH proton donors of the two aromatic rings. The frequency-dependent branching ratios observed for IRPD of cold Np + -H 2 O-Ar clusters allows the estimation of the dissociation energy of Np + -H 2 O as D 0 ∼ 2800 ± 300 cm -1 . The monohydration motif of Np + differs qualitatively from that of the benzene cation in both structure and binding energy, indicating the strong influence of the multiple aromatic rings on the hydration of PAH + cations. This difference is rationalized by natural bond orbital analysis of the ionic H-bond motif. Comparison with neutral Np-H 2 O reveals the large change in structure and bond strength of the hydrated PAHs upon ionization. While neutral Np-H 2 O is stabilized by weak π H-bonds (OHπ, π-stacking), strong cation-dipole forces favour a planar bifurcated CHO ionic H-bond in Np + -H 2 O.

Determination of chlorinated polycyclic aromatic hydrocarbons in water by solid-phase extraction coupled with gas chromatography and mass spectrometry.

PubMed

Wang, Xianli; Kang, Haiyan; Wu, Junfeng

2016-05-01

Given the potential risks of chlorinated polycyclic aromatic hydrocarbons, the analysis of their presence in water is very urgent. We have developed a novel procedure for determining chlorinated polycyclic aromatic hydrocarbons in water based on solid-phase extraction coupled with gas chromatography and mass spectrometry. The extraction parameters of solid-phase extraction were optimized in detail. Under the optimal conditions, the proposed method showed wide linear ranges (1.0-1000 ng/L) with correlation coefficients ranging from 0.9952 to 0.9998. The limits of detection and the limits of quantification were in the range of 0.015-0.591 and 0.045-1.502 ng/L, respectively. Recoveries ranged from 82.5 to 102.6% with relative standard deviations below 9.2%. The obtained method was applied successfully to the determination of chlorinated polycyclic aromatic hydrocarbons in real water samples. Most of the chlorinated polycyclic aromatic hydrocarbons were detected and 1-monochloropyrene was predominant in the studied water samples. This is the first report of chlorinated polycyclic aromatic hydrocarbons in water samples in China. The toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in the studied tap water were 9.95 ng the toxic equivalency quotient m(-3) . 9,10-Dichloroanthracene and 1-monochloropyrene accounted for the majority of the total toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in tap water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polycyclic aromatic hydrocarbons in water, sediment, soil, and plants of the Aojiang River waterway in Wenzhou, China

PubMed Central

Li, Jianwang; Shang, Xu; Zhao, Zhixu; Tanguay, Robert L.; Dong, Qiaoxiang; Huang, Changjiang

2012-01-01

The town of Shuitou was renowned as the leather capital of China because of its large-scale tanning industry, but the industry’s lack of pollution controls has caused severe damage to the local water system. This study determined 15 priority polycyclic aromatic hydrocarbons (PAHs) in water, sediment, soil, and plant samples collected from Aojiang River and its estuary. The total PAHs ranged from 910 to 1520 ng/L in water samples. The total PAH in sediments were moderate to low in comparison with other rivers and estuaries in China, but the relative proportions of PAHs per million people are high when considering the population size associated with each watershed. Ratios of fluoranthene/pyrene and PAHs with low/high molecular weight suggest a petrogenic PAH origin. The PAH composition profile in soil was similar to that in sediment with 4–6 ring PAHs being dominant. The PAHs with 2–3 rings were the dominant species in plant leaves. There were no correlations between PAHs in soils and in plants, suggesting that PAHs accumulate in plant leaves through absorption from the air. The general observation of elevated PAH concentrations in all matrix suggests a possible contribution by the local leather industry on the PAH concentrations in the Aojiang watershed. PMID:19726127

Distribution, partition and removal of polycyclic aromatic hydrocarbons (PAHs) during coking wastewater treatment processes.

PubMed

Zhang, Wanhui; Wei, Chaohai; An, Guanfeng

2015-05-01

In this study, we report the performance of a full-scale conventional activated sludge (A-O1-O2) treatment in eliminating polycyclic aromatic hydrocarbons (PAHs). Both aqueous and solid phases along with the coking wastewater treatment processes were analyzed for the presence of 18 PAHs. It was found that the target compounds occurred widely in raw coking wastewater, treated effluent and sludge samples. In the coking wastewater treatment system, 4-5 ring PAHs were the dominant compounds, while 4 rings PAHs predominated in the sludge samples. Over 98% of the PAH removal was achieved in the coking wastewater treatment plant (WWTP), with the total concentration of PAHs being 21.3 ± 1.9 μg L(-1) in the final effluent. During the coking wastewater treatment processes, the association of the lower molecular weight PAH with suspended solids was generally less than 60%, while the association of higher molecular weight PAHs was greater than 90%. High distribution efficiencies (Kdp and Kds) were found, suggesting that adsorption was the potential removal pathway of PAHs. Finally, the mass balances of PAHs in various stages of the coking WWTP were obtained, and the results indicated that adsorption to sludge was the main removal pathway for PAHs in the coking wastewater treatment processes.

Polycyclic aromatic hydrocarbon metabolic network in Mycobacterium vanbaalenii PYR-1.

PubMed

Kweon, Ohgew; Kim, Seong-Jae; Holland, Ricky D; Chen, Hongyan; Kim, Dae-Wi; Gao, Yuan; Yu, Li-Rong; Baek, Songjoon; Baek, Dong-Heon; Ahn, Hongsik; Cerniglia, Carl E

2011-09-01

This study investigated a metabolic network (MN) from Mycobacterium vanbaalenii PYR-1 for polycyclic aromatic hydrocarbons (PAHs) from the perspective of structure, behavior, and evolution, in which multilayer omics data are integrated. Initially, we utilized a high-throughput proteomic analysis to assess the protein expression response of M. vanbaalenii PYR-1 to seven different aromatic compounds. A total of 3,431 proteins (57.38% of the genome-predicted proteins) were identified, which included 160 proteins that seemed to be involved in the degradation of aromatic hydrocarbons. Based on the proteomic data and the previous metabolic, biochemical, physiological, and genomic information, we reconstructed an experiment-based system-level PAH-MN. The structure of PAH-MN, with 183 metabolic compounds and 224 chemical reactions, has a typical scale-free nature. The behavior and evolution of the PAH-MN reveals a hierarchical modularity with funnel effects in structure/function and intimate association with evolutionary modules of the functional modules, which are the ring cleavage process (RCP), side chain process (SCP), and central aromatic process (CAP). The 189 commonly upregulated proteins in all aromatic hydrocarbon treatments provide insights into the global adaptation to facilitate the PAH metabolism. Taken together, the findings of our study provide the hierarchical viewpoint from genes/proteins/metabolites to the network via functional modules of the PAH-MN equipped with the engineering-driven approaches of modularization and rationalization, which may expand our understanding of the metabolic potential of M. vanbaalenii PYR-1 for bioremediation applications.

Preparation of polydimethylsiloxane/beta-cyclodextrin/divinylbenzene coated "dumbbell-shaped" stir bar and its application to the analysis of polycyclic aromatic hydrocarbons and polycyclic aromatic sulfur heterocycles compounds in lake water and soil by high performance liquid chromatography.

PubMed

Yu, Chunhe; Yao, Zhimin; Hu, Bin

2009-05-08

A "dumbbell-shaped" stir bar was proposed to prevent the friction loss of coating during the stirring process, and thus prolonged the lifetime of stir bars. The effects of the coating components, including polydimethylsiloxane (PDMS), beta-cyclodextrin (beta-CD) and divinylbenzene (DVB) were investigated according to an orthogonal experimental design, using three polycyclic aromatic hydrocarbons (PAHs) and four polycyclic aromatic sulfur heterocycles (PASHs) as model analytes. Four kinds of stir bars coated with PDMS, PDMS/beta-CD, PDMS/DVB and PDMS/beta-CD/DVB were prepared and their extraction efficiencies for the target compounds were compared. It was demonstrated that PDMS/beta-CD/DVB-coated stir bar showed the best affinity to the studied compounds. The preparation reproducibility of PDMS/beta-CD/DVB-coated stir bar ranged from 3.2% to 15.2% (n = 6) in one batch, and 5.2% to 13.4% (n = 6) among batches. The "dumbbell-shaped" stir bar could be used for about 40 times, which were 10 extractions more than a normal stir bar. The prepared PDMS/beta-CD/DVB-coated "dumbbell-shaped" stir bar was used for stir bar sorptive extraction (SBSE) of PAHs and PASHs and the desorbed solution was introduced into HPLC-UV for subsequent analysis. The limits of detection of the proposed method for seven target analytes ranged from 0.007 to 0.103 microg L(-1), the relative standard deviations were in the range of 6.3-12.9% (n = 6, c = 40 microg L(-1)), and the enrichment factors were 19-86. The proposed method was successfully applied to the analysis of seven target analytes in lake water and soil samples.

Distribution of trace metals, aliphatic hydrocarbons and polycyclic aromatic hydrocarbons in sediment cores from the Sicily Channel and the gulf of Tunis (south-western Mediterranean Sea).

PubMed

Mzoughi, Nadia; Chouba, Lassaad

2011-01-01

Under the framework of the IAEA's Technical Co-operation project RAF7/004, international research cruises were carried out in 2004 to assess the distribution of radionuclides and micropollutants in the south-western Mediterranean Sea. Sediments samples had variable concentrations of total aliphatic hydrocarbons and polycyclic aromatic hydrocarbons ranging from 0.2 to 1.8 microg g(-1) and 26.9 to 364.4 ng g(-1), respectively, in the Sicily Channel and from 0.7 to 2.8 microg g(-1) and 14.7 to 618.1 ng g(-1), respectively, in the open sea of the Gulf of Tunis. Hydrocarbon concentrations changed with depth and were relatively high at 3 cm and 10 cm depths. The use of 'fingerprint' ratios of certain isomeric pairs of polycyclic aromatic hydrocarbons (PAH) and the proportion of 2-3 ring and 4-5 ring PAH concentrations showed that the main origins are characteristic of petroleum sources. The ranges of trace metal concentrations, expressed in microgg(-1), in the Sicily Channel and in the Gulf of Tunis, respectively, were: Hg 0.009-0.2 and 0.02-0.1; Pb 9.9-26.1 and 21.2-32.5; Cd 0.06-0.1 and 0.07-0.33; Fe 23.7-28.1 and 29.9-36.2p; Zn 83-99.5 and 83-104; Mn 309.2-752.5 and 651-814; Cu 17.1-18.5 and 33.5-51.3. Sediment metal abundances were in the order: Mn > Zn > Fe > Cu > Pb > Cd > Hg. The results showed significant differences (p < 0.001) for trace metal and hydrocarbon mean concentrations between the two cores. These concentrations are generally similar to the background levels from the Mediterranean Sea and could be affected by physico-chemical conditions and sedimentation rate as well as biodegradation.

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

PubMed

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

2016-02-01

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

Quantification of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate using stable isotope dilution liquid chromatography with atmospheric-pressure photoionization tandem mass spectrometry.

PubMed

Zhang, Xiaotao; Hou, Hongwei; Chen, Huan; Liu, Yong; Wang, An; Hu, Qingyuan

2015-09-17

A stable isotope dilution liquid chromatography with tandem mass spectrometry method for the analysis of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate was developed and validated. Compared with previously reported methods, this method has lower limits of detection (0.04-1.35 ng/cig). Additionally, the proposed method saves time, reduces the number of separation steps, and reduces the quantity of solvent needed. The new method was applied to evaluate polycyclic aromatic hydrocarbon content in 213 commercially available cigarettes in China, under the International Standardization Organization smoking regime and the Health Canadian intense smoking regime. The results showed that the total polycyclic aromatic hydrocarbon content was more than two times higher in samples from the Health Canadian intense smoking regime than in samples from the International Standardization Organization smoking regime (1189.23 vs. 2859.50 ng/cig, p<0.05). Meanwhile, the concentration of individual polycyclic aromatic hydrocarbons (and total polycyclic aromatic hydrocarbons) increased with labeled tar content in both of the tested smoking regimes. There was a positive correlation between total polycyclic aromatic hydrocarbons under the International Standardization Organization smoking regime with that under the Health Canadian intense smoking regime. The proposed liquid chromatography with tandem mass spectrometry method is satisfactory for the rapid, sensitive, and accurately quantitative evaluation of polycyclic aromatic hydrocarbon content in cigarette smoke condensate, and it can be applied to assess potential health risks from smoking. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Weathering patterns of polycyclic aromatic hydrocarbons contained in submerged Deepwater Horizon oil spill residues when re-exposed to sunlight.

PubMed

John, Gerald F; Han, Yuling; Clement, T Prabhakar

2016-12-15

The Deepwater Horizon (DWH) oil spill event released a large amount of sweet crude oil into the Gulf of Mexico (GOM). An unknown portion of this oil that arrived along the Alabama shoreline interacted with nearshore sediments and sank forming submerged oil mats (SOMs). A considerable amount of hydrocarbons, including polycyclic aromatic hydrocarbons (PAHs), were trapped within these buried SOMs. Recent studies completed using the oil spill residues collected along the Alabama shoreline have shown that several PAHs, especially higher molecular weight PAHs (four or more aromatic rings), are slowly weathering compared to the weathering levels experienced by the oil when it was floating over the GOM. In this study we have hypothesized that the weathering rates of PAHs in SOMs have slowed down because the buried oil was isolated from direct exposure to sunlight, thus hindering the photodegradation pathway. We further hypothesized that re-exposing SOMs to sunlight can reactivate various weathering reactions. Also, SOMs contain 75-95% sand (by weight) and the entrapped sand could either block direct sunlight or form large oil agglomerates with very little exposed surface area; these processes could possibly interfere with weathering reactions. To test these hypotheses, we completed controlled experiments to study the weathering patterns of PAHs in a field recovered SOM sample after re-exposing it to sunlight. Our experimental results show that the weathering levels of several higher molecular weight PAHs have slowed down primarily due to the absence of sunlight-induced photodegradation reactions. The data also show that sand particles in SOM material could potentially interfere with photodegradation reactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Recent Advances in Ring-Opening Functionalization of Cycloalkanols by C-C σ-Bond Cleavage.

PubMed

Wu, Xinxin; Zhu, Chen

2018-06-01

Cycloalkanols prove to be privileged precursors for the synthesis of distally substituted alkyl ketones and polycyclic aromatic hydrocarbons (PAHs) by virtue of cleavage of their cyclic C-C bonds. Direct functionalization of cyclobutanols to build up other chemical bonds (e. g., C-F, C-Cl, C-Br, C-N, C-S, C-Se, C-C, etc.) has been achieved by using the ring-opening strategy. Mechanistically, the C-C cleavage of cyclobutanols can be involved in two pathways: (a) transition-metal catalyzed β-carbon elimination; (b) radical-mediated 'radical clock'-type ring opening. The recent advances of our group for the ring-opening functionalization of tertiary cycloalkanols are described in this account. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Concentration and particle size distribution of polycyclic aromatic hydrocarbons formed by thermal cooking.

PubMed

Saito, E; Tanaka, N; Miyazaki, A; Tsuzaki, M

2014-06-15

The concentration and particle size distribution of 19 major polycyclic aromatic hydrocarbons (PAHs) emitted by thermal cooking were investigated. Corn, trout, beef, prawns, and pork were selected for grilling. The PAHs in the oil mist emitted when the food was grilled were collected according to particle size range and analysed by GC/MS. Much higher concentrations of PAHs were detected in the oil mist emitted by grilled pork, trout, and beef samples, which were rich in fat. The main components of the cooking exhaust were 3- and 4-ring PAHs, regardless of food type. The particle size distribution showed that almost all the PAHs were concentrated in particles with diameters of <0.43 μm. For pork, the toxic equivalent of benzo[a]pyrene accounted for 50% of the PAHs in particles with diameters of <0.43 μm. From these results, we estimated that >90% of the PAHs would reach the alveolar region of the lungs. Copyright © 2013 Elsevier Ltd. All rights reserved.

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.

Optimization of Polycyclic Aromatic Hydrocarbon (PAH) Extraction Efficiency Parameters for Sub- and Supercritical Water Extraction (SCWE) Instrument

NASA Technical Reports Server (NTRS)

Okada, Asahi A.

2005-01-01

Polycyclic aromatic hydrocarbons are a class of molecules composed of multiple, bonded benzene rings. As PAHS are believed to be present on Mars, positive confirmation of their presence on Mars is highly desirable. To extract PAHS, which have low volatility, a fluid extraction method is ideal, and one that does not utilize organic solvents is especially ideal for in situ instrumental analysis. The use of water as a solvent, which at subcritical pressures and temperatures is relatively non-Polar, has significant potential. As SCWE instruments have not yet been commercialized, all instruments are individually-built research prototypes: thus, initial efforts were intended to determine if extraction efficiencies on the JPL-built laboratory-scale SCWE instrument are comparable to differing designs built elsewhere. Samples of soil with certified reference concentrations of PAHs were extracted using SCWE as well as conventional Soxhlet extraction. Continuation of the work would involve extractions on JPL'S newer, portable SCWE instrument prototype to determine its efficiency in extracting PAHs.

FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND CARBONACEOUS SOLIDS IN GAS-PHASE CONDENSATION EXPERIMENTS

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

Jaeger, C.; Huisken, F.; Henning, Th.

2009-05-01

Carbonaceous grains represent a major component of cosmic dust. In order to understand their formation pathways, they have been prepared in the laboratory by gas-phase condensation reactions such as laser pyrolysis and laser ablation. Our studies demonstrate that the temperature in the condensation zone determines the formation pathway of carbonaceous particles. At temperatures lower than 1700 K, the condensation by-products are mainly polycyclic aromatic hydrocarbons (PAHs) that are also the precursors or building blocks for the condensing soot grains. The low-temperature condensates contain PAH mixtures that are mainly composed of volatile three to five ring systems. At condensation temperatures highermore » than 3500 K, fullerene-like carbon grains and fullerene compounds are formed. Fullerene fragments or complete fullerenes equip the nucleating particles. Fullerenes can be identified as soluble components. Consequently, condensation products in cool and hot astrophysical environments such as cool and hot asymptotic giant branch stars or Wolf-Rayet stars should be different and should have distinct spectral properties.« less

Occurrence and distribution of polycyclic aromatic hydrocarbons in surface sediments of San Diego Bay marinas.

PubMed

Neira, Carlos; Cossaboon, Jennifer; Mendoza, Guillermo; Hoh, Eunha; Levin, Lisa A

2017-01-15

Polycyclic aromatic hydrocarbons (PAHs) have garnered much attention due to their bioaccumulation, carcinogenic properties, and persistence in the environment. Investigation of the spatial distribution, composition, and sources of PAHs in sediments of three recreational marinas in San Diego Bay, California revealed significant differences among marinas, with concentrations in one site exceeding 16,000ngg -1 . 'Hotspots' of PAH concentration suggest an association with stormwater outfalls draining into the basins. High-molecular weight PAHs (4-6 rings) were dominant (>86%); the average percentage of potentially carcinogenic PAHs was high in all sites (61.4-70%) but ecotoxicological risks varied among marinas. Highly toxic benzo(a)pyrene (BaP) was the main contributor (>90%) to the total toxic equivalent quantity (TEQ) in marinas. PAHs in San Diego Bay marina sediments appear to be derived largely from pyrogenic sources, potentially from combustion products that reach the basins by aerial deposition and stormwater drainage from nearby streets and parking lots. Copyright © 2016 Elsevier Ltd. All rights reserved.

[Contamination and ecological risk assessment of polycyclic aromatic hydrocarbons in water and in Karst underground river catchment].

PubMed

Lan, Jia-Cheng; Sun, Yu-Chuan; Tian, Ping; Lu, Bing-Qing; Shi, Yang; Xu, Xin; Liang Zuo-Bing; Yang, Ping-Heng

2014-10-01

Water samples in Laolongdong underground river catchment were collected to determine the concentration, compositional profiles, and evaluate ecological risk of 16 priority polycyclic aromatic hydrocarbons (PAHs). PAHs were measured by GC/MS. The total concentrations of 16 PAH ranged from 81.5-8019 ng · L(-1) in underground river, 288.7-15,200 ng · L(-1) in karst springs, and 128.4-2,442 ng · L(-1) in surface water. Affected by waste water from Huangjueya town, concentrations of PAHs in underground river were higher than those in surface water and waste water from sinkhole. The PAHs profiles were dominated by 3 ring PAHs. There were differences of monthly variations of PAHs contents in the water, due to waste water, season and different characteristics of PAH. Surface water and waste water from sinkhole played an important role on contamination in the river. The levels of ecological risk were generally moderately polluted and heavily polluted according to all detected PAH compounds in the water.

Distribution and sources of polycyclic aromatic hydrocarbons and phthalic acid esters in water and surface sediment from the Three Gorges Reservoir.

PubMed

Lin, Li; Dong, Lei; Meng, Xiaoyang; Li, Qingyun; Huang, Zhuo; Li, Chao; Li, Rui; Yang, Wenjun; Crittenden, John

2018-07-01

After the impoundment of the Three Gorges Reservoir (TGR), the hydrological situation of the reservoir has changed greatly. The concentration and distribution of typical persistent organic pollutants in water and sediment have also changed accordingly. In this study, the concentration, distribution and potential sources of 16 polycyclic aromatic hydrocarbons (PAHs) and 6 phthalic acid esters (PAEs) during the water drawdown and impoundment periods were investigated in water and sediment from the TGR. According to our results, PAHs and PAEs showed temporal and spatial variations. The mean ΣPAH and ΣPAE concentrations in water and sediment were both higher during the water impoundment period than during the water drawdown period. The water samples from the main stream showed larger ΣPAH concentration fluctuations than those from tributaries. Both the PAH and PAE concentrations meet the Chinese national water environmental quality standard (GB 3838-2002). PAH monomers with 2-3 rings and 4 rings were dominant in water, and 4-ring and 5-6-ring PAHs were dominant in sediment. Di-n-butyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) were the dominant PAE pollutants in the TGR. DBP and DEHP had the highest concentrations in water and sediment, respectively. The main source of PAHs in water from the TGR was petroleum and emissions from coal and biomass combustion, whereas the main sources of PAHs in sediments included coal and biomass combustion, petroleum, and petroleum combustion. The main source of PAEs in water was domestic waste, and the plastics and heavy chemical industries were the main sources of PAEs in sediment. Copyright © 2017. Published by Elsevier B.V.

Retentivity, selectivity and thermodynamic behavior of polycyclic aromatic hydrocarbons on charge-transfer and hypercrosslinked stationary phases under conditions of normal phase high performance liquid chromatography.

PubMed

Jiang, Ping; Lucy, Charles A

2016-03-11

Charge-transfer and hypercrosslinked polystyrene phases offer retention and separation for polycyclic aromatic hydrocarbons (PAHs) and thus have potential for petroleum analysis. The size, shape and planarity selectivity for PAH standards on charge-transfer (DNAP column) and hypercrosslinked polystyrene (HC-Tol and 5HGN columns) phases are different under normal phase liquid chromatography (NPLC). The HC-Tol column behaves like a conventional NPLC column with low retention of PAHs. Retention of PAHs on the DNAP and 5HGN are strong and increases with the number of aromatic rings. The main retention mechanism is through π-π interactions and dipole-induced dipole interaction. Thermodynamics indicates that the retention mechanism of PAHs remains unchanged over the temperature range 20-60°C. In addition, on either DNAP or 5HGN column, both linear and bent PAHs are retained through the same mechanism. But DNAP possesses smaller π-π interaction and higher planarity selectivity than 5HGN for PAHs. This is suggestive that DNAP interacts with PAHs through a disordered phase arrangement, while 5HGN behaves as an ordered adsorption phase. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-01-01

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

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Nitrogen Heterocycles (PANHs)

NASA Technical Reports Server (NTRS)

Mattioda, A. L.; Hudgins, D. M.; Bauschlicher, C. W.; Allamandola, L. J.; Biemesderfer, C. D.; Rosi, M.

2002-01-01

The mid-infrared spectra of the nitrogen-containing heterocyclic polycyclic aromatic compounds 1-azabenz[a]-anthracene; 2-azabenz[a]anthracene; 1-azachrysene; 2-azachrysene; 4-azachrysene; 2-azapyrene, and 7,8 benzoquinoline in their neutral and cation forms were investigated. The spectra of these species isolated in an argon matrix have been measured. Band frequencies and intensities were tabulated and these data compared with spectra computed using density functional theory at the B3LYP level. The overall agreement between experiment and theory is quite good, in keeping with earlier results on homonuclear polycyclic aromatic hydrocarbons. The differences between the spectral properties of nitrogen bearing aromatics and non-substituted, neutral polycyclic aromatic hydrocarbons will be discussed.

Polycyclic aromatic hydrocarbons in Cambodian smoked fish.

PubMed

Slámová, Tereza; Fraňková, Adéla; Hubáčková, Anna; Banout, Jan

2017-12-01

More than 85% of the population in Cambodia is strongly dependent on agriculture, of which freshwater aquaculture is one of the most important sources of food production. The smoked fish represents an important source of nutrients for Cambodian population; however, it can also lead to excessive intake of polycyclic aromatic hydrocarbons (PAHs). A field survey was conducted among selected smoked fish producers near to Tonle Sap river in Kampong Chhnang province, Cambodia. The study revealed that maximal limits for benzo[a]pyrene and the sum of four PAHs given by EC 1881/2006 were exceeded 2-50 times. Such burden can lead to increased risk of development of carcinogenic diseases.

Magnetic graphene oxide as adsorbent for the determination of polycyclic aromatic hydrocarbon metabolites in human urine.

PubMed

Zhu, Linli; Xu, Hui

2014-09-01

Detection of monohydroxy polycyclic aromatic hydrocarbons metabolites in urine is an advisable and valid method to assess human environmental exposure to polycyclic aromatic hydrocarbons. In this work, novel Fe3O4/graphene oxide composites were prepared and their application in the magnetic solid-phase extraction of monohydroxy polycyclic aromatic hydrocarbons in urine was investigated by coupling with liquid chromatography and mass spectrometry. In the hybrid material, superparamagnetic Fe3O4 nanoparticles provide fast separation to simplify the analytical process and graphene oxide provides a large functional surface for the adsorption. The prepared magnetic nanocomposites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometry. The experimental conditions were optimized systematically. Under the optimal conditions, the recoveries of these compounds were in the range of 98.3-125.2%, the relative standard deviations ranged between 6.8 and 15.5%, and the limits of detection were in the range of 0.01-0.15 ng/mL. The simple, quick, and affordable method was successfully used in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities. The results indicated that the monohydroxy polycyclic aromatic hydrocarbons level in human urine can provide useful information for environmental exposure to polycyclic aromatic hydrocarbons. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioaccumulation of polycyclic aromatic compounds: 2. Modeling bioaccumulation in marine organisms chronically exposed to dispersed oil.

PubMed

Baussant, T; Sanni, S; Skadsheim, A; Jonsson, G; Børseth, J F; Gaudebert, B

2001-06-01

Within the frame of a large environmental study, we report on a research program that investigated the potential for bioaccumulation and subsequent effect responses in several marine organisms exposed to chronic levels of dispersed crude oil. Body burden can be estimated from kinetic parameters (rate constants for uptake and elimination), and appropriate body burden-effect relationships may improve assessments of environmental risks or the potential for such outcomes following chronic discharges at sea. We conducted a series of experiments in a flow-through system to describe the bioaccumulation kinetics of polycyclic aromatic hydrocarbons (PAH) at low concentrations of dispersed crude oils. Mussels (Mytilus edulis) and juvenile turbot (Scophthalmus maximus) were exposed for periods ranging from 8 to 21 d. Postexposure, the organisms were kept for a period of 9 to 10 d in running seawater to study elimination processes. Rate constants of uptake (k1) and elimination (k2) of the PAHs during and following exposure were calculated using a first-order kinetic model that assumed a decrease of the substances in the environment over time. The estimated bioconcentration factor was calculated from the ratio of k1/k2. The kinetic parameters of two-, three-, and four-ring PAHs in mussel and fish are compared with estimates based on hydrophobicity alone, expressed by the octanol-water partition coefficient, Kow (partitioning theory). A combination of reduced bioavailability of PAHs from oil droplets and degradation processes of PAHs in body tissues seems to explain discrepancies between kinetic rates based on Kow and actual kinetic rates measured in fish. Mussels showed a pattern more in compliance with the partitioning theory.

Determination of semi-volatile and particle-associated polycyclic aromatic hydrocarbons in Stockholm air with emphasis on the highly carcinogenic dibenzopyrene isomers

NASA Astrophysics Data System (ADS)

Masala, Silvia; Lim, Hwanmi; Bergvall, Christoffer; Johansson, Christer; Westerholm, Roger

2016-09-01

The concentrations of polycyclic aromatic hydrocarbons (PAHs) have been determined in the gaseous phase and in various particulate matter (PM) size fractions at different locations in and outside of Stockholm, Sweden, representative of street level, urban and rural background. The focus has been on the seldom determined but highly carcinogenic dibenzopyrene isomers (DBPs) dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene. PAHs with 3 rings were found to be mainly associated with the vapor phase (>90%) whereas PAHs with 5-6 rings were mostly associated with particulate matter (>92%) and the 4-ringed PAHs partitioned between the two phases. PAH abundance was determined to be in the order street level > urban background > rural background with the PM10 street level 2010 mean of benzo[a]pyrene (B[a]P) reaching 0.24 ng/m3, well below the EU annual limit value of 1 ng/m3. In addition, higher PAH concentrations were found in the sub-micron particle fraction (PM1) as compared to the super-micron fraction (PM1-10) with the abundance in PM1 varying between 57 and 86% of the total PAHs. The B[a]P equivalent concentrations derived for DB[a,l]P and total DBPs exceeded 1-2 and 2-4 times, respectively, that of B[a]P at the four sampling sites; therefore underestimation of the cancer risk posed by PAHs in air could be made if the DBPs were not considered in risk assessment using the toxic equivalency approach, whilst the high correlation (p < 0.001) found in the relative concentrations supports the use of B[a]P as a marker substance for assessment of the carcinogenic risk associated to PAHs. However, the big difference in concentration ratios of B[a]P and the DBPs between the present study and some literature data calls for further research to evaluate the temporal and spatial invariance of the B[a]P/DBP ratios.

Synthesis of condensed phases containing polycyclic aromatic hydrocarbons fullerenes and nanotubes

DOEpatents

Reilly, Peter T. A.

2004-10-19

The invention relates to methods for producing polycyclic aromatic hydrocarbons, fullerenes, and nanotubes, comprising: a. heating at least one carbon-containing material to form a condensed phase comprising at least one polycyclic aromatic hydrocarbon; b. collecting at least some of the condensed phase; c. reacting the condensed phase to form fullerenes and/or nanotubes.

Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Thomas, J. D.; Witt, A. N.

2006-01-01

The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

Polycyclic aromatic hydrocarbons at fire stations: firefighters' exposure monitoring and biomonitoring, and assessment of the contribution to total internal dose.

PubMed

Oliveira, Marta; Slezakova, Klara; Alves, Maria José; Fernandes, Adília; Teixeira, João Paulo; Delerue-Matos, Cristina; Pereira, Maria do Carmo; Morais, Simone

2017-02-05

This work characterizes levels of eighteen polycyclic aromatic hydrocarbons (PAHs) in the breathing air zone of firefighters during their regular work shift at eight Portuguese fire stations, and the firefighters' total internal dose by six urinary monohydroxyl metabolites (OH-PAHs). Total PAHs (ΣPAHs) concentrations varied widely (46.4-428ng/m 3 ), mainly due to site specificity (urban/rural) and characteristics (age and layout) of buildings. Airborne PAHs with 2-3 rings were the most abundant (63.9-95.7% ΣPAHs). Similarly, urinary 1-hydroxynaphthalene and 1-hydroxyacenaphthene were the predominant metabolites (66-96% ΣOH-PAHs). Naphthalene contributed the most to carcinogenic ΣPAHs (39.4-78.1%) in majority of firehouses; benzo[a]pyrene, the marker of carcinogenic PAHs, accounted with 1.5-10%. Statistically positive significant correlations (r≥0.733, p≤0.025) were observed between ΣPAHs and urinary ΣOH-PAHs for firefighters of four fire stations suggesting that, at these sites, indoor air was their major exposure source of PAHs. Firefighter's personal exposure to PAHs at Portuguese fire stations were well below the existent occupational exposure limits. Also, the quantified concentrations of post-shift urinary 1-hydroxypyrene in all firefighters were clearly lower than the benchmark level (0.5μmol/mol) recommended by the American Conference of Governmental Industrial Hygienists. Copyright © 2016 Elsevier B.V. All rights reserved.

Treatability assessment of polycyclic aromatic hydrocarbons contaminated marine sediments using permanganate, persulfate and Fenton oxidation processes.

PubMed

Shih, Yu-Jen; Binh, Nguyen Thanh; Chen, Chiu-Wen; Chen, Chih-Feng; Dong, Cheng-Di

2016-05-01

Various chemical oxidation techniques, such as potassium permanganate (KMnO4), sodium persulfate (Na2S2O8), Fenton (H2O2/Fe(2+)), and the modified persulfate and Fenton reagents (activated by ferrous complexes), were carried out to treat marine sediments that were contaminated with polycyclic aromatic hydrocarbons (PAHs) and dredged from Kaohsiung Harbor in Taiwan. Experimental results revealed that KMnO4 was the most effective of the tested oxidants in PAH degradation. Owing to the high organic matter content in the sediment that reduced the efficiencies of Na2S2O8 and regular Fenton reactions, a large excess of oxidant was required. Nevertheless, KH2PO4, Na4P2O7 and four chelating agents (EDTA, sodium citrate, oxalic acid, and sodium oxalate) were utilized to stabilize Fe(II) in activating the Na2S2O8 and Fenton oxidations, while Fe(II)-citrate remarkably promoted the PAH degradation. Increasing the molecular weight and number of rings of PAH did not affect the overall removal efficiencies. The correlation between the effectiveness of the oxidation processes and the physicochemical properties of individual PAH was statistically analyzed. The data implied that the reactivity of PAH (electron affinity and ionization potential) affected its treatability more than did its hydrophobicity (Kow, Koc and Sw), particularly using experimental conditions under which PAHs could be effectively oxidized. Copyright © 2016 Elsevier Ltd. All rights reserved.

CYP63A2, a catalytically versatile fungal P450 monooxygenase capable of oxidizing higher-molecular-weight polycyclic aromatic hydrocarbons, alkylphenols, and alkanes.

PubMed

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E; Yadav, Jagjit S

2013-04-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills).

CYP63A2, a Catalytically Versatile Fungal P450 Monooxygenase Capable of Oxidizing Higher-Molecular-Weight Polycyclic Aromatic Hydrocarbons, Alkylphenols, and Alkanes

PubMed Central

Syed, Khajamohiddin; Porollo, Aleksey; Lam, Ying Wai; Grimmett, Paul E.

2013-01-01

Cytochrome P450 monooxygenases (P450s) are known to oxidize hydrocarbons, albeit with limited substrate specificity across classes of these compounds. Here we report a P450 monooxygenase (CYP63A2) from the model ligninolytic white rot fungus Phanerochaete chrysosporium that was found to possess a broad oxidizing capability toward structurally diverse hydrocarbons belonging to mutagenic/carcinogenic fused-ring higher-molecular-weight polycyclic aromatic hydrocarbons (HMW-PAHs), endocrine-disrupting long-chain alkylphenols (APs), and crude oil aliphatic hydrocarbon n-alkanes. A homology-based three-dimensional (3D) model revealed the presence of an extraordinarily large active-site cavity in CYP63A2 compared to the mammalian PAH-oxidizing (CYP3A4, CYP1A2, and CYP1B1) and bacterial aliphatic-hydrocarbon-oxidizing (CYP101D and CYP102A1) P450s. This structural feature in conjunction with ligand docking simulations suggested potential versatility of the enzyme. Experimental characterization using recombinantly expressed CYP63A2 revealed its ability to oxidize HMW-PAHs of various ring sizes, including 4 rings (pyrene and fluoranthene), 5 rings [benzo(a)pyrene], and 6 rings [benzo(ghi)perylene], with the highest enzymatic activity being toward the 5-ring PAH followed by the 4-ring and 6-ring PAHs, in that order. Recombinant CYP63A2 activity yielded monohydroxylated PAH metabolites. The enzyme was found to also act as an alkane ω-hydroxylase that oxidized n-alkanes with various chain lengths (C9 to C12 and C15 to C19), as well as alkyl side chains (C3 to C9) in alkylphenols (APs). CYP63A2 showed preferential oxidation of long-chain APs and alkanes. To our knowledge, this is the first P450 identified from any of the biological kingdoms that possesses such broad substrate specificity toward structurally diverse xenobiotics (PAHs, APs, and alkanes), making it a potent enzyme biocatalyst candidate to handle mixed pollution (e.g., crude oil spills). PMID:23416995

Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

PubMed

Ugochukwu, Uzochukwu C; Manning, David A C; Fialips, Claire I

2014-09-01

Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil. Copyright © 2014 Elsevier Ltd. All rights reserved.

Parking lot sealcoat: An unrecognized source of urban polycyclic aromatic hydrocarbons

USGS Publications Warehouse

Mahler, B.J.; Van Metre, P.C.; Bashara, T.J.; Wilson, J.T.; Johns, D.A.

2005-01-01

Polycyclic aromatic hydrocarbons (PAHs) are a ubiquitous contaminant in urban environments. Although numerous sources of PAHs to urban runoff have been identified, their relative importance remains uncertain. We show that a previously unidentified source of urban PAHs, parking lot sealcoat, may dominate loading of PAHs to urban water bodies in the United States. Particles in runoff from parking lots with coal-tar emulsion sealcoat had mean concentrations of PAHs of 3500 mg/kg, 65 times higher than the mean concentration from unsealed asphalt and cement lots. Diagnostic ratios of individual PAHs indicating sources are similar for particles from coal-tar emulsion sealed lots and suspended sediment from four urban streams. Contaminant yields projected to the watershed scale for the four associated watersheds indicate that runoff from sealed parking lots could account for the majority of stream PAH loads.

Seasonal atmospheric deposition and air-sea gas exchange of polycyclic aromatic hydrocarbons over the Yangtze River Estuary, East China Sea: Implications for source-sink processes

NASA Astrophysics Data System (ADS)

Jiang, Yuqing; Lin, Tian; Wu, Zilan; Li, Yuanyuan; Li, Zhongxia; Guo, Zhigang; Yao, Xiaohong

2018-04-01

In this work, air samples and surface seawater samples covering four seasons from March 2014 to January 2015 were collected from a background receptor site in the YRE to explore the seasonal fluxes of air-sea gas exchange and dry and wet deposition of 15 polycyclic aromatic hydrocarbons (PAHs) and their source-sink processes at the air-sea interface. The average dry and wet deposition fluxes of 15 PAHs were estimated as 879 ± 1393 ng m-2 d-1 and 755 ± 545 ng m-2 d-1, respectively. Gaseous PAH release from seawater to the atmosphere averaged 3114 ± 1999 ng m-2 d-1 in a year round. The air-sea gas exchange of PAHs was the dominant process at the air-sea interface in the YRE as the magnitude of volatilization flux of PAHs exceeded that of total dry and wet deposition. The gas PAH exchange flux was dominated by three-ring PAHs, with the highest value in summer and lowest in winter, indicating a marked seasonal variation owing to differences in Henry's law constants associated with temperature, as well as wind speed and gaseous-dissolved gradient among seasons. Based on the simplified mass balance estimation, a net 11 tons y-1 of PAHs (mainly three-ring PAHs) were volatilized from seawater to the atmosphere in a ∼20,000 km2 area in the YRE. Other than the year-round Yangtze River input and ocean ship emissions, the selective release of low-molecular-weight PAHs from bottom sediments in winter due to resuspension triggered by the East Asian winter monsoon is another potential source of PAHs. This work suggests that the source-sink processes of PAHs at the air-sea interface in the YRE play a crucial role in regional cycling of PAHs.

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

PubMed

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

2003-01-01

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

Sources, fate, and effects of PAHs in shallow water environments: a review with special reference to small watercraft

USGS Publications Warehouse

Albers, P.H.; Kennish, Michael J.

2002-01-01

Polycyclic aromatic hydrocarbons (PAHs) are aromatic hydrocarbons with two to seven fused carbon (benzene) rings that can have substituted groups attached. Shallow coastal, estuarine, lake, and river environments receive PAHs from treated wastewater, stormwater runoff, petroleum spills and natural seeps, recreational and commercial boats, natural fires, volcanoes, and atmospheric deposition of combustion products. Abiotic degradation of PAHs is caused by photooxidation, photolysis in water, and chemical oxidation. Many aquatic microbes, plants, and animals can metabolize and excrete ingested PAHs; accumulation is associated with poor metabolic capabilities, high lipid content, and activity patterns or distributions that coincide with high concentrations of PAHs. Resistance to biological transformation increases with increasing number of carbon rings. Four- to seven-ring PAHs are the most difficult to metabolize and the most likely to accumulate in sediments. Disturbance by boating activity of sediments, shorelines, and the surface microlayer of water causes water column re-entry of recently deposited or concentrated PAHs. Residence time for PAHs in undisturbed sediment exceeds several decades. Toxicity of PAHs causes lethal and sublethal effects in plants and animals, whereas some substituted PAHs and metabolites of some PAHs cause mutations, developmental malformations, tumors, and cancer. Environmental concentrations of PAHs in water are usually several orders of magnitude below levels that are acutely toxic, but concentrations can be much higher in sediment. The best evidence for a link between environmental PAHs and induction of cancerous neoplasms is for demersal fish in areas with high concentrations of PAHs in the sediment.

Bioaccumulation of polycyclic aromatic hydrocarbons in bivalves from Sugarland Run and the Potomac River

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

Barber, T.R.; Lauren, D.J.; Dimitry, J.A.

1995-12-31

A bioaccumulation study was conducted following a release of Fuel Oil {number_sign}2 into Sugarland Run, a small northern Virginia stream. Caged clams (Corbicula sp.) were placed in 3 downstream locations and 2 upstream reference areas for an exposure period of approximately 28 days. In addition, resident clams from the Potomac River were sampled at the start of the study and at 4 and 8 weeks. Chemical fingerprinting techniques were employed to identify spill-related polycyclic aromatic hydrocarbons (PAHs) and to differentiate these compounds from background sources of contamination. The greatest concentration of spill-related PAHs (2 and 3-ring compounds) were measured inmore » clams placed immediately downstream of the spill site, and tissue concentrations systematically decreased with distance from the spill site. PAHs that were not related to Fuel Oil {number_sign}2 were found in all clams and accounted for up to 90% of the total body burden at downstream locations. Furthermore, the highest concentrations of 4-, 5-, and 6-ring PAH were found at the upstream reference location, and indicated an important source of PAHs into the environment. Body burdens measured in this study were compared to ambient concentrations reported for bivalves from a variety of environments. Tissue concentrations were also compared to concentrations that have been reported to cause adverse biological effects.« less

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.

Replication of a carcinogenic nitropyrene DNA lesion by human Y-family DNA polymerase

PubMed Central

Kirouac, Kevin N.; Basu, Ashis K.; Ling, Hong

2013-01-01

Nitrated polycyclic aromatic hydrocarbons are common environmental pollutants, of which many are mutagenic and carcinogenic. 1-Nitropyrene is the most abundant nitrated polycyclic aromatic hydrocarbon, which causes DNA damage and is carcinogenic in experimental animals. Error-prone translesion synthesis of 1-nitropyrene–derived DNA lesions generates mutations that likely play a role in the etiology of cancer. Here, we report two crystal structures of the human Y-family DNA polymerase iota complexed with the major 1-nitropyrene DNA lesion at the insertion stage, incorporating either dCTP or dATP nucleotide opposite the lesion. Polι maintains the adduct in its active site in two distinct conformations. dCTP forms a Watson–Crick base pair with the adducted guanine and excludes the pyrene ring from the helical DNA, which inhibits replication beyond the lesion. By contrast, the mismatched dATP stacks above the pyrene ring that is intercalated in the helix and achieves a productive conformation for misincorporation. The intra-helical bulky pyrene mimics a base pair in the active site and facilitates adenine misincorporation. By structure-based mutagenesis, we show that the restrictive active site of human polη prevents the intra-helical conformation and A-base misinsertions. This work provides one of the molecular mechanisms for G to T transversions, a signature mutation in human lung cancer. PMID:23268450

Multimedia Model for Polycyclic Aromatic Hydrocarbons (PAHs) and Nitro-PAHs in Lake Michigan

PubMed Central

2015-01-01

Polycyclic aromatic hydrocarbon (PAH) contamination in the U.S. Great Lakes has long been of concern, but information regarding the current sources, distribution, and fate of PAH contamination is lacking, and very little information exists for the potentially more toxic nitro-derivatives of PAHs (NPAHs). This study uses fugacity, food web, and Monte Carlo models to examine 16 PAHs and five NPAHs in Lake Michigan, and to derive PAH and NPAH emission estimates. Good agreement was found between predicted and measured PAH concentrations in air, but concentrations in water and sediment were generally under-predicted, possibly due to incorrect parameter estimates for degradation rates, discharges to water, or inputs from tributaries. The food web model matched measurements of heavier PAHs (≥5 rings) in lake trout, but lighter PAHs (≤4 rings) were overpredicted, possibly due to overestimates of metabolic half-lives or gut/gill absorption efficiencies. Derived PAH emission rates peaked in the 1950s, and rates now approach those in the mid-19th century. The derived emission rates far exceed those in the source inventories, suggesting the need to reconcile differences and reduce uncertainties. Although additional measurements and physiochemical data are needed to reduce uncertainties and for validation purposes, the models illustrate the behavior of PAHs and NPAHs in Lake Michigan, and they provide useful and potentially diagnostic estimates of emission rates. PMID:25373871

Nanofiller Presence Enhances Polycyclic Aromatic Hydrocarbon (PAH) Profile on Nanoparticles Released during Thermal Decomposition of Nano-enabled Thermoplastics: Potential Environmental Health Implications.

PubMed

Singh, Dilpreet; Schifman, Laura Arabella; Watson-Wright, Christa; Sotiriou, Georgios A; Oyanedel-Craver, Vinka; Wohlleben, Wendel; Demokritou, Philip

2017-05-02

Nano-enabled products are ultimately destined to reach end-of-life with an important fraction undergoing thermal degradation through waste incineration or accidental fires. Although previous studies have investigated the physicochemical properties of released lifecycle particulate matter (called LCPM) from thermal decomposition of nano-enabled thermoplastics, critical questions about the effect of nanofiller on the chemical composition of LCPM still persist. Here, we investigate the potential nanofiller effects on the profiles of 16 Environmental Protection Agency (EPA)-priority polycyclic aromatic hydrocarbons (PAHs) adsorbed on LCPM from thermal decomposition of nano-enabled thermoplastics. We found that nanofiller presence in thermoplastics significantly enhances not only the total PAH concentration in LCPM but most importantly also the high molecular weight (HMW, 4-6 ring) PAHs that are considerably more toxic than the low molecular weight (LMW, 2-3 ring) PAHs. This nano-specific effect was also confirmed during in vitro cellular toxicological evaluation of LCPM for the case of polyurethane thermoplastic enabled with carbon nanotubes (PU-CNT). LCPM from PU-CNT shows significantly higher cytotoxicity compared to PU which could be attributed to its higher HMW PAH concentration. These findings are crucial and make the case that nanofiller presence in thermoplastics can significantly affect the physicochemical and toxicological properties of LCPM released during thermal decomposition.

Spatial Distribution of Polycyclic Aromatic Hydrocarbon (PAH) Concentrations in Soils from Bursa, Turkey.

PubMed

Karaca, Gizem

2016-02-01

The objectives of this study were to identify regional variations in soil polycyclic aromatic hydrocarbon (PAH) contamination in Bursa, Turkey, and to determine the distributions and sources of various PAH species and their possible sources. Surface soil samples were collected from 20 different locations. The PAH concentrations in soil samples were analyzed using gas chromatography-mass spectrometry (GC-MS). The total PAH concentrations (∑12 PAH) varied spatially between 8 and 4970 ng/g dry matter (DM). The highest concentrations were measured in soils taken from traffic+barbecue+ residential areas (4970 ng/g DM) and areas with cement (4382 ng/g DM) and iron-steel (4000 ng/g DM) factories. In addition, the amounts of ∑7 carcinogenic PAH ranged from 1 to 3684 ng/g DM, and between 5 and 74 % of the total PAHs consisted of such compounds. Overall, 4-ring PAH compounds (Fl, Pyr, BaA and Chr) were dominant in the soil samples, with 29-82 % of the ∑12 PAH consisting of 4-ring PAH compounds. The ∑12 BaPeq values ranged from 0.1 to 381.8 ng/g DM. Following an evaluation of the molecular diagnostic ratios, it was concluded that the PAH pollution in Bursa soil was related to pyrolytic sources; however, the impact of petrogenic sources should not be ignored.

High-resolution depositional records of polycyclic aromatic hydrocarbons in the central continental shelf mud of the East China Sea.

PubMed

Guo, Zhigang; Lin, Tian; Zhang, Gan; Yang, Zuosheng; Fang, Ming

2006-09-01

A well-placed 210Pb-dated sediment core extracted from the distal mud in the central continental shelf of the East China Sea is used to reconstruct the high-resolution atmospheric depositional record of polycyclic aromatic hydrocarbons (PAHs), believed to be transported mainly from China in the past 200 years due to the East Asian Monsoon. Total PAHs (TPAHs), based on the 16 USEPA priority PAHs, range from 27 in 1788 to 132 ng g(-1) in 2001. TPAH variation in the core reflects energy usage changes and follows closely the historical economic development in China. PAHs in the core are dominantly pyrogenic in source, i.e., they are mainly from the incomplete combustion of coal and biomass burning. Several individual PAHs suggest that contribution from incomplete petroleum combustion has increased during recent years. Analysis of the 2 + 3 ring and the 5 + 6 ring PAHs and principle component analysis provide more evidence in the change in the energy structure, especially after 1978 when China embarked on the "Reform and Open" Policy, indicating the transformation from an agricultural to an industrial economy of China. The historical profile of PAH distribution in the study area is obviously different from the United States and Europe due to their difference in energy structure and economic development stages.

Tandem enyne metathesis-Diels-Alder reaction for construction of natural product frameworks.

PubMed

Rosillo, Marta; Domínguez, Gema; Casarrubios, Luis; Amador, Ulises; Pérez-Castells, Javier

2004-03-19

Enynes connected through aromatic rings are used as substrates for metathesis reactions. The reactivity of three ruthenium carbene complexes is compared. The resulting 1,3-dienes are suitable precursors of polycyclic structures via a Diels-Alder process. Some domino RCM-Diels-Alder reactions are performed, suggesting a possible beneficial effect of the ruthenium catalyst in the cycloaddition process. Other examples require Lewis acid cocatalyst. When applied to aromatic ynamines or enamines, a new synthesis of vinylindoles is achieved. Monitorization of several metathesis reactions with NMR shows the different behavior for ruthenium catalysts. New carbenic species are detected in some reactions with an important dependence on the solvent used.

Detection of the aromatic molecule benzonitrile (c-C6H5CN) in the interstellar medium

NASA Astrophysics Data System (ADS)

McGuire, Brett A.; Burkhardt, Andrew M.; Kalenskii, Sergei; Shingledecker, Christopher N.; Remijan, Anthony J.; Herbst, Eric; McCarthy, Michael C.

2018-01-01

Polycyclic aromatic hydrocarbons and polycyclic aromatic nitrogen heterocycles are thought to be widespread throughout the universe, because these classes of molecules are probably responsible for the unidentified infrared bands, a set of emission features seen in numerous Galactic and extragalactic sources. Despite their expected ubiquity, astronomical identification of specific aromatic molecules has proven elusive. We present the discovery of benzonitrile (c-C6H5CN), one of the simplest nitrogen-bearing aromatic molecules, in the interstellar medium. We observed hyperfine-resolved transitions of benzonitrile in emission from the molecular cloud TMC-1. Simple aromatic molecules such as benzonitrile may be precursors for polycyclic aromatic hydrocarbon formation, providing a chemical link to the carriers of the unidentified infrared bands.

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.

Polycyclic Aromatic Hydrocarbons: A Critical Review of Environmental Occurrence and Bioremediation.

PubMed

Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Oluwatoyin; Jackson, Vanessa Angela

2017-10-01

The degree of polycyclic aromatic hydrocarbon contamination of environmental matrices has increased over the last several years due to increase in industrial activities. Interest has surrounded the occurrence and distribution of polycyclic aromatic hydrocarbons for many decades because they pose a serious threat to the health of humans and ecosystems. The importance of the need for sustainable abatement strategies to alleviate contamination therefore cannot be overemphasised, as daily human activities continue to create pollution from polycyclic aromatic hydrocarbons and impact the natural environment. Globally, attempts have been made to design treatment schemes for the remediation and restoration of contaminated sites. Several techniques and technologies have been proposed and tested over time, the majority of which have significant limitations. This has necessitated research into environmentally friendly and cost-effective clean-up techniques. Bioremediation is an appealing option that has been extensively researched and adopted as it has been proven to be relatively cost-effective, environmentally friendly and is publicly accepted. In this review, the physicochemical properties of some priority polycyclic aromatic hydrocarbons, as well as the pathways and mechanisms through which they enter the soil, river systems, drinking water, groundwater and food are succinctly examined. Their effects on human health, other living organisms, the aquatic ecosystem, as well as soil microbiota are also elucidated. The persistence and bioavailability of polycyclic aromatic hydrocarbons are discussed as well, as they are important factors that influence the rate, efficiency and overall success of remediation. Bioremediation (aerobic and anaerobic), use of biosurfactants and bioreactors, as well as the roles of biofilms in the biological treatment of polycyclic aromatic hydrocarbons are also explored.

Polycyclic Aromatic Hydrocarbons: A Critical Review of Environmental Occurrence and Bioremediation

NASA Astrophysics Data System (ADS)

Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Oluwatoyin; Jackson, Vanessa Angela

2017-10-01

The degree of polycyclic aromatic hydrocarbon contamination of environmental matrices has increased over the last several years due to increase in industrial activities. Interest has surrounded the occurrence and distribution of polycyclic aromatic hydrocarbons for many decades because they pose a serious threat to the health of humans and ecosystems. The importance of the need for sustainable abatement strategies to alleviate contamination therefore cannot be overemphasised, as daily human activities continue to create pollution from polycyclic aromatic hydrocarbons and impact the natural environment. Globally, attempts have been made to design treatment schemes for the remediation and restoration of contaminated sites. Several techniques and technologies have been proposed and tested over time, the majority of which have significant limitations. This has necessitated research into environmentally friendly and cost-effective clean-up techniques. Bioremediation is an appealing option that has been extensively researched and adopted as it has been proven to be relatively cost-effective, environmentally friendly and is publicly accepted. In this review, the physicochemical properties of some priority polycyclic aromatic hydrocarbons, as well as the pathways and mechanisms through which they enter the soil, river systems, drinking water, groundwater and food are succinctly examined. Their effects on human health, other living organisms, the aquatic ecosystem, as well as soil microbiota are also elucidated. The persistence and bioavailability of polycyclic aromatic hydrocarbons are discussed as well, as they are important factors that influence the rate, efficiency and overall success of remediation. Bioremediation (aerobic and anaerobic), use of biosurfactants and bioreactors, as well as the roles of biofilms in the biological treatment of polycyclic aromatic hydrocarbons are also explored.

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.

AROMATIC AND POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN A LAMINAR PREMIXED N-BUTANE FLAME. (R825412)

EPA Science Inventory

Abstract

Experimental and detailed chemical kinetic modeling work has been performed to investigate aromatic and polycyclic aromatic hydrocarbon (PAH) formation pathways in a premixed, rich, sooting, n-butane_¯oxygen_¯argon burner s...

ACTIVATION OF OYSTER DEFENSES BY ENVIRONMENTAL CONTAMINANTS

EPA Science Inventory

Four field studies performed on eastern oysters Crassostrea virginica support a hypothesis that Cu, Zn, and perhaps butyltins and polycyclic aromatic hydrocarbons (PAH) can stimulate hemopoiesis, hemocyte locomotion and hemocyte bactericidal capacity. The first study found circul...

Parking lot sealcoat: an unrecognized source of urban polycyclic aromatic hydrocarbons

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

Barbara J. Mahler; Peter C. Van Metre; Thomas J. Bashara

2005-08-01

Polycyclic aromatic hydrocarbons (PAHs) are a ubiquitous contaminant in urban environments. Although numerous sources of PAHs to urban runoff have been identified, their relative importance remains uncertain. The authors show that a previously unidentified source of urban PAHs, parking lot sealcoat, may dominate loading of PAHs to urban water bodies in the United States. Particles in runoff from parking lots with coal-tar emulsion sealcoat had mean concentrations of PAHs of 3500 mg/kg, 65 times higher than the mean concentration from unsealed asphalt and cement lots. Diagnostic ratios of individual PAHs indicating sources are similar for particles from coal-tar emulsion sealedmore » lots and suspended sediment from four urban streams. Contaminant yields projected to the watershed scale for the four associated watersheds indicate that runoff from sealed parking lots could account for the majority of stream PAH loads. 35 refs., 6 figs., 2 tabs.« less

Hydrogenated Benzene in Circumstellar Environments: Insights into the Photostability of Super-hydrogenated PAHs

NASA Astrophysics Data System (ADS)

Quitián-Lara, Heidy M.; Fantuzzi, Felipe; Nascimento, Marco A. C.; Wolff, Wania; Boechat-Roberty, Heloisa M.

2018-02-01

Polycyclic aromatic hydrocarbons (PAHs), comprised of fused benzene (C6H6) rings, emit infrared radiation (3–12 μm) due to the vibrational transitions of the C–H bonds of the aromatic rings. The 3.3 μm aromatic band is generally accompanied by the band at 3.4 μm assigned to the vibration of aliphatic C–H bonds of compounds such as PAHs with an excess of peripheral H atoms (H n –PAHs). Herein we study the stability of fully hydrogenated benzene (or cyclohexane, C6H12) under the impact of stellar radiation in the photodissociation region (PDR) of NGC 7027. Using synchrotron radiation and time-of-flight mass spectrometry, we investigated the ionization and dissociation processes at energy ranges of UV (10–200 eV) and soft X-rays (280–310 eV). Density Functional Theory (DFT) calculations were used to determine the most stable structures and the relevant low-lying isomers of singly charged C6H12 ions. Partial Ion Yield (PIY) analysis gives evidence of the higher tendency toward dissociation of cyclohexane in comparison to benzene. However, because of the high photoabsorption cross-section of benzene at the C1s resonance edge, its photodissociation and photoionization cross-sections are enhanced, leading to a higher efficiency of dissociation of benzene in the PDR of NGC 7027. We suggest that a similar effect is experienced by PAHs in X-ray photon-rich environments, which ultimately acts as an auxiliary protection mechanism of super-hydrogenated polycyclic hydrocarbons. Finally, we propose that the single photoionization of cyclohexane could enhance the abundance of branched molecules in interstellar and circumstellar media.

Large Abundances of Polycyclic Aromatic Hydrocarbons in Titan's Upper Atmosphere

NASA Technical Reports Server (NTRS)

Lopez-Puertas, M.; Dinelli, B. M.; Adriani, A.; Funke, B.; Garcia-Comas, M.; Moriconi, M. L.; D'Aversa, E.; Boersma, C.; Allamandola, L. J.

2013-01-01

In this paper, we analyze the strong unidentified emission near 3.28 micron in Titan's upper daytime atmosphere recently discovered by Dinelli et al.We have studied it by using the NASA Ames PAH IR Spectroscopic Database. The polycyclic aromatic hydrocarbons (PAHs), after absorbing UV solar radiation, are able to emit strongly near 3.3 micron. By using current models for the redistribution of the absorbed UV energy, we have explained the observed spectral feature and have derived the vertical distribution of PAH abundances in Titan's upper atmosphere. PAHs have been found to be present in large concentrations, about (2-3) × 10(exp 4) particles / cubic cm. The identified PAHs have 9-96 carbons, with a concentration-weighted average of 34 carbons. The mean mass is approx 430 u; the mean area is about 0.53 sq. nm; they are formed by 10-11 rings on average, and about one-third of them contain nitrogen atoms. Recently, benzene together with light aromatic species as well as small concentrations of heavy positive and negative ions have been detected in Titan's upper atmosphere. We suggest that the large concentrations of PAHs found here are the neutral counterpart of those positive and negative ions, which hence supports the theory that the origin of Titan main haze layer is located in the upper atmosphere.

Influence of ozone and meteorological parameters on levels of polycyclic aromatic hydrocarbons in the air

NASA Astrophysics Data System (ADS)

Pehnec, Gordana; Jakovljević, Ivana; Šišović, Anica; Bešlić, Ivan; Vađić, Vladimira

2016-04-01

Concentrations of ten polycyclic aromatic hydrocarbons (PAHs) in the PM10 particle fraction were measured together with ozone and meteorological parameters at an urban site (Zagreb, Croatia) over a one-year period. Data were subjected to regression analysis in order to determine the relationship between the measured pollutants and selected meteorological variables. All of the PAHs showed seasonal variations with high concentrations in winter and autumn and very low concentrations during summer and spring. All of the ten PAHs concentrations also correlated well with each other. A statistically significant negative correlation was found between the concentrations of PAHs and ozone concentrations and concentrations of PAHs and temperature, as well as a positive correlation between concentrations of PAHs and PM10 mass concentration and relative humidity. Multiple regression analysis showed that concentrations of PM10 and ozone, temperature, relative humidity and pressure accounted for 43-70% of PAHs variability. Concentrations of PM10 and temperature were significant variables for all of the measured PAH's concentrations in all seasons. Ozone concentrations were significant for only some of the PAHs, particularly 6-ring PAHs.

Increased concentrations of polycyclic aromatic hydrocarbons in Alpine streams during annual snowmelt: investigating effects of sampling method, site characteristics, and meteorology.

PubMed

Shahpoury, Pourya; Hageman, Kimberly J; Matthaei, Christoph D; Alumbaugh, Robert E; Cook, Michelle E

2014-10-07

Silicone passive samplers and macroinvertebrates were used to measure time-integrated concentrations of polycyclic aromatic hydrocarbons (PAHs) in alpine streams during annual snowmelt. The three sampling sites were located near a main highway in Arthur's Pass National Park in the Southern Alps of New Zealand. A similar set of PAH congeners, composed of 2-4 rings, were found in silicone passive samplers and macroinvertebrates. The background PAH concentrations were similar at all sites, implying that proximity to the highway did not affect concentrations. In passive samplers, an increase of PAH concentrations by up to seven times was observed during snowmelt. In macroinvertebrates, the concentration changes were moderate; however, macroinvertebrate sampling did not occur during the main pulse observed in the passive samplers. The extent of vegetation in the catchment appeared to affect the concentration patterns seen at the different stream sites. A strong correlation was found between PAH concentrations in passive samplers and the amount of rainfall in the study area, indicating that the washout of contaminants from snowpack by rainfall was an important process.

Effects of root exudates on gel-beads/reeds combination remediation of high molecular weight polycyclic aromatic hydrocarbons.

PubMed

Tian, Weijun; Zhao, Jing; Zhou, Yuhang; Qiao, Kaili; Jin, Xin; Liu, Qing

2017-01-01

Changes in root exudates, including low molecular weight organic acids (LMWOAs), amino acids and sugars, in rhizosphere soils during the gel-beads/reeds combination remediation for high molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) and the degree of the effects on HMW-PAH biodegradation were evaluated in this study. The results showed that the gel-beads/reeds combination remediation notably increased the removal rates of pyrene, benzo(a)pyrene and indeno(1,2,3-cd)pyrene (65.0-68.9%, 60.0-68.5% and 85.2-85.9%, respectively). During the removal of HMW-PAHs, the LMWOAs, particularly maleic acid, enhanced the biodegradation of HMW-PAHs. Arginine and trehalose monitored in reed root exudates promoted the growth of plants and microorganisms and then improved the removal of HMW-PAHs, especially pyrene. However, the contribution of reed root exudates on degradation of 5- and 6-ring PAHs was minor. These results indicated that the utilization of root exudates was certainly not the only important trait for the removal of HMW-PAHs. Copyright © 2016 Elsevier Inc. All rights reserved.

Effect of the ultrasound-Fenton oxidation process with the addition of a chelating agent on the removal of petroleum-based contaminants from soil.

PubMed

Li, Ying; Li, Fangmin; Li, Fanxiu; Yuan, Fuqian; Wei, Pingfang

2015-12-01

The effects of ultrasonic irradiation, the chelating agent modified Fenton reaction, and a combination of ultrasound and the Fenton method in removing petroleum contaminants from a soil were studied. The results showed that the contaminant removal rate of the Fenton treatment combined with an oxalic acid chelating agent was 55.6% higher than that without a chelating agent. The average removal rate of the contaminants using the ultrasound-Fenton treatment was 59.0% higher than that without ultrasonic treatment. A combination of ultrasound and an Fe(2+)/Fe(3+)-oxalate complex-modified Fenton reagent resulted in significantly higher removal rates of n-alkanes (C(n)H(2n+2), n < 28), isoprenoid hydrocarbons, aromatic hydrocarbons, and saturated polycyclic terpenes compared with the ultrasound treatment alone or the Fenton method. The Fenton reaction and the ultrasound-Fenton treatment can unselectively remove multiple components of residual hydrocarbons and a number of benzene rings in polycyclic aromatic hydrocarbons. The chemistry of the heterocyclic compounds and the position and number of substituents can affect the degradation process.

Advances in the field of high‐molecular‐weight polycyclic aromatic hydrocarbon biodegradation by bacteria

PubMed Central

Kanaly, Robert A.; Harayama, Shigeaki

2010-01-01

Summary Interest in understanding prokaryotic biotransformation of high‐molecular‐weight polycyclic aromatic hydrocarbons (HMW PAHs) has continued to grow and the scientific literature shows that studies in this field are originating from research groups from many different locations throughout the world. In the last 10 years, research in regard to HMW PAH biodegradation by bacteria has been further advanced through the documentation of new isolates that represent diverse bacterial types that have been isolated from different environments and that possess different metabolic capabilities. This has occurred in addition to the continuation of in‐depth comprehensive characterizations of previously isolated organisms, such as Mycobacterium vanbaalenii PYR‐1. New metabolites derived from prokaryotic biodegradation of four‐ and five‐ring PAHs have been characterized, our knowledge of the enzymes involved in these transformations has been advanced and HMW PAH biodegradation pathways have been further developed, expanded upon and refined. At the same time, investigation of prokaryotic consortia has furthered our understanding of the capabilities of microorganisms functioning as communities during HMW PAH biodegradation. PMID:21255317

Soil-borne polycyclic aromatic hydrocarbons in El Paso, Texas: Analysis of a potential problem in the United States/Mexico border region

PubMed Central

De La Torre-Roche, Roberto J.; Lee, Wen-Yee; Campos-Díaz, Sandra I.

2009-01-01

Ultrasonic extraction followed by Stir Bar Sorptive Extraction (SBSE) and thermal desorption inline coupled with Gas Chromatography and Mass Spectrometry (TD/GC/MS)was used to perform a comprehensive determination of soil-borne polycyclic aromatic hydrocarbons (PAHs) in El Paso, Texas. The method provided good sensitivity and faster processing time for the analysis. The total PAHs in El Paso soil ranged from 0.1 to 2225.5 µg kg−1. Although the majority of PAH concentrations did not exceed the soil screening levels regulated by the United States Environmental Protection Agency, the existence of PAHs in this ecosystem is ubiquitous. Naphthalene were found in 100% of the soil samples; while the heavy PAHs (five- and six-ring) were not often detected and mostly remained in closer proximity to industrial areas and major traffic points. The results ruled out the possibility of petroleum refining as the significant source of local soil-borne PAH contamination, but they suggested that the PAHs found in El Paso soil were closely linked to human activities and possible other industrial processes. PMID:18768257

Identification of sources of polycyclic aromatic hydrocarbons based on concentrations in soils from two sides of the Himalayas between China and Nepal.

PubMed

Luo, Wei; Gao, Jiajia; Bi, Xiang; Xu, Lan; Guo, Junming; Zhang, Qianggong; Romesh, Kumar Y; Giesy, John P; Kang, Shichang

2016-05-01

To understand distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in the Himalayas, 77 soil samples were collected from the northern side of the Himalayas, China (NSHC), and the southern side of the Himalayas, Nepal (SSHN), based on altitude, land use and possible trans-boundary transport of PAHs driven by wind from Nepal to the Tibetan Plateau, China. Soils from the SSHN had mean PAH concentration greater than those from the NSHC. Greater concentrations of PAHs in soils were mainly distributed near main roads and agricultural and urban areas. PAHs with 2-3 rings were the most abundant PAHs in the soils from the Himalayas. Concentrations of volatile PAHs were significantly and positively correlated with altitude. Simulations of trajectories of air masses indicated that distributions of soil PAH concentrations were associated with the cyclic patterns of the monsoon. PAH emissions from traffic and combustion of biomass or coal greatly contributed to concentrations of PAHs in soils from the Himalayas. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

Modelli, Alberto; Mussoni, Laura; Fabbri, Daniele

2006-05-25

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

MORPHOLOGICAL TRANSFORMATION AND DNA ADDUCT FORMATION BY BENZ[J]ACEANTHRYLENE AND ITS METABOLITES IN C3H1OT1/2CL8 CELLS: EVIDENCE FOR BOTH CYCLOPENTA-RING AND BAY REGION METABOLIC ACTIVATION PATHWAYS

EPA Science Inventory

Benz[j]aceanthrylene (B[j]A), a cyclopenta-fused polycyclic aromatic hydrocarbon (CP-PAH) related to 3-methylcholanthrene, has been studied to identify the major routes of metabolic activation in transformable C3H1OT1/2CLB (C3H1OT1/2) mouse embryo fibroblasts in culture. he morph...

Polycyclic aromatic hydrocarbons in model bacterial membranes - Langmuir monolayer studies.

PubMed

Broniatowski, Marcin; Binczycka, Martyna; Wójcik, Aneta; Flasiński, Michał; Wydro, Paweł

2017-12-01

High molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) are persistent organic pollutants which due to their limited biodegradability accumulate in soils where their increased presence can lead to the impoverishment of the decomposer organisms. As very hydrophobic PAHs easily penetrate cellular membranes of soil bacteria and can be incorporated therein, changing the membrane fluidity and other functions which in consequence can lead to the death of the organism. The structure and size of PAH molecule can be crucial for its membrane activity; however the correlation between PAH structure and its interaction with phospholipids have not been investigated so far. In our studies we applied phospholipid Langmuir monolayers as model bacterial membranes and investigated how the incorporation of six structurally different PAH molecules change the membrane texture and physical properties. In our studies we registered surface pressure and surface potential isotherms upon the monolayer compression, visualized the monolayer texture with the application of Brewster angle microscopy and searched the ordering of the film-forming molecules with molecular resolution with the application of grazing incidence X-ray diffraction (GIXD) method. It turned out that the phospholipid-PAH interactions are strictly structure dependent. Four and five-ring PAHs of the angular or cluster geometry can be incorporated into the model membranes changing profoundly their textures and fluidity; whereas linear or large cluster PAHs cannot be incorporated and separate from the lipid matrix. The observed phenomena were explained based on structural similarities of the applied PAHs with membrane steroids and hopanoids. Copyright © 2017. Published by Elsevier B.V.

Effects of polycyclic aromatic hydrocarbons on microbial community structure and PAH ring hydroxylating dioxygenase gene abundance in soil.

PubMed

Sawulski, Przemyslaw; Clipson, Nicholas; Doyle, Evelyn

2014-11-01

Development of successful bioremediation strategies for environments contaminated with recalcitrant pollutants requires in-depth knowledge of the microorganisms and microbial processes involved in degradation. The response of soil microbial communities to three polycyclic aromatic hydrocarbons, phenanthrene (3-ring), fluoranthene (4-ring) and benzo(a)pyrene (5-ring), was examined. Profiles of bacterial, archaeal and fungal communities were generated using molecular fingerprinting techniques (TRFLP, ARISA) and multivariate statistical tools were employed to interpret the effect of PAHs on community dynamics and composition. The extent and rate of PAH removal was directly related to the chemical structure, with the 5-ring PAH benzo(a)pyrene degraded more slowly than phenathrene or fluoranthene. Bacterial, archaeal and fungal communities were all significantly affected by PAH amendment, time and their interaction. Based on analysis of clone libraries, Actinobacteria appeared to dominate in fluoranthene amended soil, although they also represented a significant portion of the diversity in phenanthrene amended and unamended soils. In addition there appeared to be more γ-Proteobacteria and less Bacteroidetes in soil amended with either PAH compared to the control. The soil bacterial community clearly possessed the potential to degrade PAHs as evidenced by the abundance of PAH ring hydroxylating (PAH-RHDα) genes from both gram negative (GN) and gram positive (GP) bacteria in PAH-amended and control soils. Although the dioxygenase gene from GP bacteria was less abundant in soil than the gene associated with GN bacteria, significant (p < 0.001) increases in the abundance of the GP PAH-RHDα gene were observed during phenanthrene and fluoranthene degradation, whereas there was no significant difference in the abundance of the GN PAH-RHDα gene during the course of the experiment. Few studies to-date have examined the effect of pollutants on more than one microbial community in soil. The current study provides information on the response of soil bacterial, archaeal and fungal communities during the degradation of three priority pollutants and contributes to a knowledge base that can inform the development of effective bioremediation strategies for contaminated sites.

Determination of polycyclic aromatic hydrocarbons with molecular weight 300 and 302 in environmental-matrix standard reference materials by gas chromatography/mass spectrometry.

PubMed

Schubert, Patricia; Schantz, Michele M; Sander, Lane C; Wise, Stephen A

2003-01-15

An analytical approach based on gas chromatography/ mass spectrometry (GC/MS) is presented for the measurement of polycyclic aromatic hydrocarbons with molecular weight (MW) 300 and 302 in environmental samples. Three different GC stationary phases [5% and 50% phenyl methylpolysiloxane and dimethyl (50% liquid crystalline) polysiloxane] were compared, and retention indexes (RI) are given for 23 individual MW 302 isomers. Identification of MW 300 and 302 isomers in four environmental-matrix Standard Reference Materials (SRMs) (SRM 1597, coal tar extract; SRM 1648 and SRM 1649a, air particulate matter; and SRM 1941, marine sediment) was based on the comparison of RI data and mass spectra from authentic standards. Dibenzo[a,l]pyrene, which is of considerable interest because of its high carcinogenicity, was identified and quantified in the four environmental-matrix SRMs. A total of 23 isomers of MW 302 and four isomers of MW 300 were quantified in four different environmental-matrix SRMs, and the results are compared to previously reported results based on liquid chromatography with fluorescence detection.

Up-regulation of CYP1A1 and phase II enzymes by 5-ring isomeric polycyclic aromatic hydrocarbons in precision-cut rat hepatic slices: Importance of molecular shape.

PubMed

Pushparajah, Daphnee; Lewis, Dfv; Ioannides, Costas

2017-04-01

The objectives of the present study were two-fold: (a) to evaluate the role of molecular shape on the interaction of polycyclic aromatic hydrocarbons (PAHs) with the Ah receptor and CYP1A1 upregulation, and (b) to evaluate the potential of PAHs to induce epoxide hydrolase and glutathione S-transferase, two major enzymes involved in their metabolism. In order to achieve these objectives, precision-cut rat liver slices were incubated with a range of concentrations of seven 5-ring isomeric PAHs, namely benzo[c]chrysene, benzo[b]chrysene, benzo[g]chrysene, dibenzo[a,j]anthracene, dibenzo[a,c]anthracene, picene and pentacene, for 24h. All compounds, with the exception of pentacene, elevated the O-deethylation of ethoxyresorufin, an activity associated with CYP1A1; induction of this enzyme by the various PAHs correlated with their avidity for the Ah receptor. None of the PAHs studied increased epoxide hydrolase activity, monitored using benzo[a]pyrene 4,5-oxide. Of the seven PAHs, only benzo[g]chrysene elevated glutathione S-transferase activity, measured using 1-chloro-2,4-dinitrobenzene or 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole as substrates. No relationship could be established between length or length/width and interaction with the Ah receptor and CYP1A1 up-regulation indicating that other structural or electronic factors are likely to be more important. Finally, 5-ring PAHs are poor inducers of the epoxide hydrolase and glutathione S-transferase enzyme systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of 15 polycyclic aromatic hydrocarbons in aquatic products by solid-phase extraction and GC-MS.

PubMed

Liu, Qiying; Guo, Yuanming; Sun, Xiumei; Hao, Qing; Cheng, Xin; Zhang, Lu

2018-02-22

We propose a method for the simultaneous determination of 15 kinds of polycyclic aromatic hydrocarbons in marine samples (muscle) employing gas chromatography with mass spectrometry after saponification with ultrasound-assisted extraction and solid-phase extraction. The experimental conditions were optimized by the response surface method. In addition, the effects of different lyes and extractants on polycyclic aromatic hydrocarbons extraction were discussed, and saturated sodium carbonate was first used as the primary saponification reaction and extracted with 10 mL of ethyl acetate and secondly 1 mol/L of sodium hydroxide and 10 mL of n-hexane were used to achieve better results. The average recovery was 67-112%. Satisfactory data showed that the method has good reproducibility with a relative standard deviation of <13%. The detection limits of polycyclic aromatic hydrocarbons were 0.02-0.13 ng/g. Compared with other methods, this method has the advantages of simple pretreatment, low solvent consumption, maximum polycyclic aromatic hydrocarbons extraction, the fast separation speed, and the high extraction efficiency. It is concluded that this method meets the batch processing requirements of the sample and can also be used to determine polycyclic aromatic hydrocarbons in other high-fat (fish, shrimp, crab, shellfish) biological samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization and determination of polycyclic aromatic hydrocarbons in biochar-based fertilizers.

PubMed

Chen, Ping; Zhou, Hui; Gan, Jay; Sun, Mingxing; Shang, Guofeng; Liu, Liang; Shen, Guoqing

2015-03-01

The agronomic benefit of biochar has attracted widespread attention to biochar-based fertilizers. However, the inevitable presence of polycyclic aromatic hydrocarbons in biochar is a matter of concern because of the health and ecological risks of these compounds. The strong adsorption of polycyclic aromatic hydrocarbons to biochar complicates their analysis and extraction from biochar-based fertilizers. In this study, we optimized and validated a method for determining the 16 priority polycyclic aromatic hydrocarbons in biochar-based fertilizers. Results showed that accelerated solvent extraction exhibited high extraction efficiency. Based on a Box-Behnken design with a triplicate central point, accelerated solvent extraction was used under the following optimal operational conditions: extraction temperature of 78°C, extraction time of 17 min, and two static cycles. The optimized method was validated by assessing the linearity of analysis, limit of detection, limit of quantification, recovery, and application to real samples. The results showed that the 16 polycyclic aromatic hydrocarbons exhibited good linearity, with a correlation coefficient of 0.996. The limits of detection varied between 0.001 (phenanthrene) and 0.021 mg/g (benzo[ghi]perylene), and the limits of quantification varied between 0.004 (phenanthrene) and 0.069 mg/g (benzo[ghi]perylene). The relative recoveries of the 16 polycyclic aromatic hydrocarbons were 70.26-102.99%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of semipermeable membrane devices for long-term monitoring of polycyclic aromatic hydrocarbons at various stages of drinking water treatment.

PubMed

Pogorzelec, Marta; Piekarska, Katarzyna

2018-08-01

The primary goal of the presented study was the investigation of occurrence and concentration of sixteen selected polycyclic aromatic hydrocarbons in samples from various stages of water treatment and verification of the applicability of semi-permeable membrane devices in the monitoring of drinking water. Another objective was to verify if weather seasons affect the concentration and complexity of PAHs. For these purposes, semipermeable membrane devices were installed in a surface water treatment plant located in Lower Silesia (Poland). Samples were collected monthly over a period of one year. To determine the effect of water treatment on PAH concentrations, four sampling sites were selected: raw water input, a stream of water in the pipe just before ozonation, treated water output and water after passing through the distribution system. After each month of sampling, SPMDs were exchanged for fresh ones and prepared for instrumental analysis. Concentrations of polycyclic aromatic hydrocarbons were determined by high-performance liquid chromatography (HPLC). The presented study indicates that semipermeable membrane devices can be an effective tool for the analysis of drinking water, in which organic micropollutants occur at very low concentrations. Copyright © 2018 Elsevier B.V. All rights reserved.

Proximity effects in the electron impact mass spectra of 2-substituted benzazoles

NASA Astrophysics Data System (ADS)

Chantler, Thomas; Perrin, Victoria L.; Donkor, Rachel E.; Cawthorne, Richard S.; Bowen, Richard D.

2004-08-01

The 70 eV electron impact mass spectra of a wide range of 2-substituted benzazoles are reported and discussed. Particular attention is paid to the mechanistic significance and analytical utility of [M-H]+ and [M-X]+ signals in the spectra of benzazoles in which the 2-substituent contains a terminal aryl group with one or more substituents, X. Loss of H[radical sign] or X[radical sign] occurs preferentially from an ortho-position from ionized 2-benzylbenzimidazoles, 2-phenethylbenzimidazoles, 2-styrylbenzimidazoles, 2-styrylbenzoxazoles and 2-styrylbenzothiazoles. In the three styrylbenzazole series, the [M-H]+ and/or [M-X]+ signals dominate the spectra. This unusually facile loss of H[radical sign] or X[radical sign] may be attributed to a proximity effect, in which cyclization of the ionized molecule is followed by elimination of an ortho-substituent to give an exceptionally stable polycyclic ion. Formation of a new five- or six-membered ring by the proximity effect occurs rapidly; cyclization to a seven-membered ring takes place rather less readily; but formation of a ring with only four atoms or more than seven atoms is not observed to a significant extent. The proximity effect competes effectively with loss of a methyl radical by simple cleavage of an ethyl, isopropyl and even a t-butyl group in the pendant aromatic ring of ionized 2-(4-alkylstyryl)benzazoles.

Chemistry and catalysis of coal liquefaction catalytic and thermal upgrading of coal liquid and hydrogenation of CO to produce fuels. Quarterly progress report, July-September 1980

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

Wiser, W.H.

1981-02-01

Studies on the basic properties of supported sulfide catalysts showed that different supports have a profound influence on catalytic activities of CoMo catalysts. The three functions of hydrodesulfurization, hydrogenation and cracking were differently affected depending on the support used and the manner of preparation of the catalyst. Also, incorporation of additives to the support showed that the different catalytic functions can be selectively affected. A systematic study concerned with catalytic cracking of coal-derived liquids, viz., an SRC-II middle-heavy distillate and four hydrotreated SRC-II products was carried out in the range of 375 to 500/sup 0/C (LHSV, 0.2 to 3.9 h/supmore » -1/). Hydrotreatment, even to a limited extent, results in a remarkable improvement in the yield of gasoline-range products from the SRC-II distillate. This improvement is ascribed to: (a) hydrogenolysis reactions leading to lower molecular weight feedstock components and (b) limited hydrogenation of aromatic rings leading to polycyclic feed components with sufficient concentration of hydroaromatic rings needed for effective cracking. The results with model compounds and the data on hydrogen consumption during hydrotreatment of SRC-II liquids indicate that for tricyclic, tetracyclic, and pentacyclic coal-liquid components the optimal concentration of hydroaromatic rings for effective subsequent cracking is at least two rings per molecule.« less

Quantum coherent π-electron rotations in a non-planar chiral molecule induced by using a linearly polarized UV laser pulse

NASA Astrophysics Data System (ADS)

Mineo, Hirobumi; Fujimura, Yuichi

2015-06-01

We propose an ultrafast quantum switching method of π-electron rotations, which are switched among four rotational patterns in a nonplanar chiral aromatic molecule (P)-2,2’- biphenol and perform the sequential switching among four rotational patterns which are performed by the overlapped pump-dump laser pulses. Coherent π-electron dynamics are generated by applying the linearly polarized UV pulse laser to create a pair of coherent quasidegenerated excited states. We also plot the time-dependent π-electron ring current, and discussed ring current transfer between two aromatic rings.

A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames

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

Wang, H.; Frenklach, M.

1997-07-01

A computational study was performed for the formation and growth of polycyclic aromatic hydrocarbons (PAHs) in laminar premixed acetylene and ethylene flames. A new detailed reaction mechanism describing fuel pyrolysis and oxidation, benzene formation, and PAH mass growth and oxidation is presented and critically tested. It is shown that the reaction model predicts reasonably well the concentration profiles of major and intermediate species and aromatic molecules in a number of acetylene and ethylene flames reported in the literature. It is demonstrated that reactions of n-C{sub 4}H{sub x} + C{sub 2}H{sub 2} leading to the formation of one-ring aromatics are asmore » important as the propargyl recombination, and hence must be included in kinetic modeling of PAH formation in hydrocarbon flames. It is further demonstrated that the mass growth of PAHs can be accounted for by the previously proposed H-abstraction-C{sub 2}H{sub 2}-addiction mechanism.« less

Formation of highly oxygenated organic molecules from aromatic compounds

NASA Astrophysics Data System (ADS)

Molteni, Ugo; Bianchi, Federico; Klein, Felix; El Haddad, Imad; Frege, Carla; Rossi, Michel J.; Dommen, Josef; Baltensperger, Urs

2018-02-01

Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

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

NASA Technical Reports Server (NTRS)

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-11-01

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

A divergent route to core- and peripherally functionalized diazacoronenes that act as colorimetric and fluorescence proton sensors

DOE PAGES

He, Bo; Dai, Jing; Zherebetskyy, Danylo; ...

2015-03-31

Combining core annulation and peripheral group modification, we have demonstrated a divergent synthesis of a family of highly functionalized coronene derivatives from a readily accessible dichlorodiazaperylene intermediate. Various reactions, such as aromatic nucleophilic substitution, Kumada coupling and Suzuki coupling proceed effectively on α-positions of the pyridine sites, giving rise to alkoxy, thioalkyl, alkyl or aryl substituted polycyclic aromatic hydrocarbons. In addition to peripheral group modulation, the aromatic core structures can be altered by annulation with thiophene or benzene ring systems. Corresponding single crystal X-ray diffraction and optical studies indicate that the heteroatom linkages not only impact the solid state packing,more » but also significantly influence the optoelectronic properties. Moreover, these azacoronene derivatives display significant acid-induced spectroscopic changes, suggesting their great potential as colorimetric and fluorescence proton sensors.« less

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.

Quantification of the carcinogenic effect of polycyclic aromatic hydrocarbons in used engine oil by topical application onto the skin of mice.

PubMed

Grimmer, G; Dettbarn, G; Brune, H; Deutsch-Wenzel, R; Misfeld, J

1982-01-01

The purpose of this investigation was to identify the substances mainly responsible for the carcinogenic effect of used engine oil from gasoline engines using topical application as a carcinogen-specific bioassay. This was performed by comparison of the tumorigenic effect of single fractions with that of an unseparated sample of the lubricating oil. The probit analysis of the results shows: 1) The used engine oil, from gasoline-driven automobiles, investigated provoked local tumors after long-term application to the dorsal skin of mice. The incidence of carcinoma depended on the dose of the oil. 2) The fraction of the polycyclic aromatic hydrocarbons (PAH) containing more than three rings accounts for about 70% of the total carcinogenicity in the case of crankcase oil. This fraction constitutes only up to 1.14% by weight of the total oil sample. 3) The content of benzo(a)pyrene (216.8 mg/kg) accounts for 18% of the total carcinogenicity of the used oil. 4) Regarding the reduced carcinogenicity of the oil sample, which was reconstituted from all fractions, it seems possible that some of the carcinogenic substances were lost due to volatility, with evaporation of the solvents from the oil-fractionation processes. 5) Regarding the small effect of the PAH-free fraction, as well as the equal carcinogenic effects of the PAH-fraction (containing more than three rings) and the reconstituted oil sample, no hints for a co-carcinogenic activity were obtained.

Long-term effects of discharges of produced water the marine environment from petroleum-related activities at Sonda de Campeche, Gulf of México.

PubMed

Schifter, I; González-Macías, C; Salazar-Coria, L; Sánchez-Reyna, G; González-Lozano, C

2015-11-01

Produced water from offshore oil platforms is a major source of oil and related chemicals into the sea. The large volume and high salinity of produced water could pose severe environmental impacts upon inadequate disposal. This study is based on direct field sampling of effluents released into the ocean in the years 2003 and 2013 at the Sonda de Campeche located in the southern part of the Gulf of Mexico. Metals and hydrocarbons were characterized in water, sediments, and fish tissues at the discharge site and compared with those obtained at two reference sites. Chemicals that exceeded risk-based concentrations in the discharge included the metals As, Pb, Cd, and Cr, and a variety of compounds polycyclic aromatic hydrocarbon (PAHs), including naphthalene, fluorenes, and low molecular weight PAHs. The values of low to high molecular weight polycyclic aromatic hydrocarbon (PAHs), and carbon preference index indicate that hydrocarbons in sediments of the discharge zone are originated from the produced water and combustion sources. Fish tissues at the discharge zone and reference site are contaminated with PAHs, dominated by 2- and 3-rings; 4-ring accounted for less than 1% of total PAHs (TPAHs) in 2003, but increased to 7% in 2013. Results suggest that, from 2003 to 2013, discharges of produced water have had a non-negligible impact on ecosystems at a regional level, so the possibility of subtle, cumulative effects from operational discharges should not be ignored.

Distributions and Sources of Polycyclic Aromatic Hydrocarbons (PAHs) in Soils around a Chemical Plant in Shanxi, China.

PubMed

Jiao, Haihua; Wang, Qi; Zhao, Nana; Jin, Bo; Zhuang, Xuliang; Bai, Zhihui

2017-10-09

Background : Yearly the Shanxi coal chemical industry extracts many coal resources, producing at the same time many polycyclic aromatic hydrocarbons (PAHs) that are emitted as by-products of coal incomplete combustion. Methods : Sixty-six soil samples collected from 0 to 100 cm vertical sections of three different agricultural (AS), roadside (RS) and park (PS) functional soils around a chemical plant in Shanxi, China were analyzed for the presence of the 16 priority control PAHs. Results : The total concentrations (∑16PAHs) varied in a range of 35.4-116 mg/kg, 5.93-66.5 mg/kg and 3.87-76.0 mg/kg for the RS, PS and AS surface soil, respectively, and 5-ring PAHs were found to be dominant (44.4-49.0%), followed by 4-ring PAHs (15.9-24.5%). Moreover, the average value of ∑16PAHs decreased with the depth, 7.87 mg/kg (0-25 cm), 4.29 mg/kg (25-50 cm), 3.00 mg/kg (50-75 cm), 2.64 mg/kg (75-100 cm) respectively, in PS and AS soil vertical sections. Conclusions : The PAH levels in the studied soils were the serious contamination level (over 1.00 mg/kg) according to the Soils Quality Guidelines. The carcinogenic PAHs (ΣBPAHsBapeq) were approximately 14.8 times higher than the standard guideline level (0.60 mg/kg) and 90.3% of PAHs were produced by coal/wood/grass combustion processes.

Surfactant-Enhanced Desorption and Biodegradation of Polycyclic Aromatic Hydrocarbons in Contaminated Soil

PubMed Central

Zhu, Hongbo; Aitken, Michael D.

2010-01-01

We evaluated two nonionic surfactants, one hydrophobic (Brij 30) and one hydrophilic (C12E8), for their ability to enhance the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil after it had been treated in an aerobic bioreactor. The effects of each surfactant were evaluated at doses corresponding to equilibrium aqueous-phase concentrations well above the surfactant’s critical micelle concentration (CMC), slightly above the CMC, and below the CMC. The concentrations of all 3- and 4-ring PAHs were significantly lower in the soil amended with Brij 30 at the two lower doses compared to controls, whereas removal of only the 3-ring PAHs was significantly enhanced at the highest Brij 30 dose. In contrast, C12E8 did not enhance PAH removal at any dose. In the absence of surfactant, <5% of any PAH desorbed from the soil over an 18-d period. Brij 30 addition at the lowest dose significantly increased the desorption of most PAHs, whereas the addition of C12E8 at the lowest dose actually decreased the desorption of all PAHs. These findings suggest that the effects of the two surfactants on PAH biodegradation could be explained by their effects on PAH bioavailability. Overall, this study demonstrates that the properties of the surfactant and its dose relative to the corresponding aqueous-phase concentration are important factors in designing systems for surfactant-enhanced bioremediation of PAH-contaminated soils in which PAH bioavailability is limited. PMID:20586488

Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity.

PubMed

Castelli, Francesco; Micieli, Dorotea; Ottimo, Sara; Minniti, Zelica; Sarpietro, Maria Grazia; Librando, Vito

2008-10-01

To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.

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

PubMed

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

2017-10-08

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

THE EFFECTS OF EQUIVALENCE RATIO ON THE FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND SOOT IN PREMIXED ETHANE FLAMES. (R825412)

EPA Science Inventory

Abstract

The formation of polycyclic aromatic hydrocarbons (PAH) and soot has been investigated in atmospheric-pressure, laminar, ethane/oxygen/argon premixed flames as a function of mixture equivalence ratio. Mole fraction profiles of major products, trace aromatics, ...

Human Exposures to PAHs: an Eastern United States Pilot Study

EPA Science Inventory

Personal exposure monitoring for select polycyclic aromatic hydrocarbons (PAHs) was performed as part of the National Human Exposure Assessment Survey (NHEXAS) Pilot Study in Baltimore, MD and in four surrounding counties (NHEXAS-Maryland). An objective of this effort was to esta...

Polycyclic aromatic hydrocarbons in urban soil of Novi Sad, Serbia: occurrence and cancer risk assessment.

PubMed

Škrbić, Biljana D; Đurišić-Mladenović, Nataša; Tadić, Đorđe J; Cvejanov, Jelena Đ

2017-07-01

Contents of 16 polycyclic aromatic hydrocarbons were analyzed in 30 soil samples from 15 locations in Novi Sad, Serbia, assessing for the first time the corresponding health risks in the Serbian urban zone. Total concentrations were in the range of 22-2247 μg kg -1 , with a mean and median value of 363 and 200 μg kg -1 , respectively. Comparison with the relevant maximum allowed contents proposed by the Serbian government and with the Dutch target values implied that soils from the urban area of Novi Sad were "suitable as residential soils" and that no intervention would be needed if the current levels were retained. Seven diagnostic ratios were calculated, indicating the pyrogenic sources of PAHs as the dominant. Cancer risks in humans via accidental ingestion, inhalation of soil particles, and dermal contact with soil were estimated. Cancer risk for soil ingestion by children was the highest. The total lifetime carcinogenic risk as sum of individual cancer risks for seven carcinogenic polycyclic aromatic hydrocarbons was within the range 10 -4 to 10 -6 , indicating acceptable risks at 30 and 47% of sites for children and adults, respectively. However, for the rest of the samples, total lifetime cancer risk was >10 -4 indicating over the acceptable risk, even though the contents in soil were not of concern as the comparison with the environmental guidance previously showed. This could be explained by (a) the dominant concentrations of higher molecular weight compounds with 4 to 6 rings, among which there are compounds with higher toxicity equivalents, but also with (b) the extreme conditions used for the conservative risk assessment under maximal exposure frequency, exposure time, and ingestion rates.

Suspect screening of OH-PAHs and non-target screening of other organic compounds in wood smoke particles using HR-Orbitrap-MS.

PubMed

Avagyan, Rozanna; Åberg, Magnus; Westerholm, Roger

2016-11-01

Wood combustion has been shown to contribute significantly to emissions of polycyclic aromatic hydrocarbons and hydroxylated polycyclic aromatic hydrocarbons, compounds with toxic and carcinogenic properties. However, only a small number of hydroxylated polycyclic aromatic hydrocarbons have been determined in particles from wood combustion, usually compounds with available reference standards. In this present study, suspect and non-target screening strategies were applied to characterize the wood smoke particles from four different wood types and two combustion conditions with respect to hydroxylated polycyclic aromatic hydrocarbons and other organic compounds. In the suspect screening, 32 peaks corresponding to 12 monohydroxylated masses were tentatively identified by elemental composition assignments and matching of isotopic pattern and fragments. More than one structure was suggested for most of the measured masses. Statistical analysis was performed on the non-target screening data in order to single out significant peaks having intensities that depend on the wood type and/or combustion condition. Significant peaks were found in both negative and positive ionization modes, with unique peaks for each wood type and combustion condition, as well as a combination of both factors. Furthermore, structural elucidation of some peaks was done by comparing the spectra in the samples with spectra found in the spectral databases. Six compounds were tentatively identified in positive ionization mode, and 19 in negative ionization mode. The results in this present study demonstrate that there are significant overall differences in the chemistry of wood smoke particles that depends on both the wood type and the combustion condition used. Copyright © 2016 Elsevier Ltd. All rights reserved.

Emissions of particle-phase polycyclic aromatic hydrocarbons (PAHs) in the Fu Gui-shan Tunnel of Nanjing, China

NASA Astrophysics Data System (ADS)

Chen, Fei; Hu, Wei; Zhong, Qin

2013-04-01

Real-world vehicle emission factors for PM10 (particulate matter with aerodynamic diameter smaller than 10 μm) and particle-phase polycyclic aromatic hydrocarbons (PAHs) from mixed vehicles were quantified in the Fu Gui-shan Tunnel of Nanjing during summer and winter of 2010. Concentrations of PM10 and sixteen particle phase polycyclic aromatic hydrocarbons (PAHs) in the entrance and exit of the tunnel were studied. The results showed that the four most abundant particular phase polycyclic aromatic hydrocarbons (PAHs) of motor vehicle were benzo[ghi]perylene, benzo[k]fluoranthene, benz[a]anthracene and benzo[a]pyrene. The emission factors for PM10 and particle-phase PAHs were 687 mg veh- 1 km- 1 and 18.853 mg veh- 1 km- 1 in summer, 714 mg veh- 1 km- 1 and 20.374 mg veh- 1 km- 1 in winter. Higher particle-phase PAH emission factors were found to be associated with a high proportion of diesel-fueled vehicles (DV). The estimated PM10 emission factor of gasoline-fueled vehicles (GV) was 513 mg veh- 1 km- 1 and the value for DV was 914 mg veh- 1 km- 1, while EFDV of particulate PAH (31.290 mg veh- 1 km- 1) was nearly 4 times higher than EFGV (9.310 mg veh- 1 km- 1). The five highest emission factors of diesel-fueled vehicles (DV) were benzo[ghi]perylene, benzo[k]fluoranthene, Indeno[1,2,3-cd]pyrene, benz[a]anthracene and benzo[a]pyrene, which was similarly found in the gasoline-fueled vehicles (GV). The sum of these five emission factors accounted for ~ 69% of the total particle-phase PAH of DV and ~ 67% of GV.

MULTISUBSTRATE BIODEGRADATION KINETICS FOR BINARY AND COMPLEX MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Biodegradation kinetics were studied for binary and complex mixtures of nine polycyclic aromatic hydrocarbons (PAHs): naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2-ethylnaphthalene, phenanthrene, anthracene, pyrene, fluorene and fluoranthene. Discrepancies between the ...

Polycyclic aromatic hydrocarbons associated with airborne particulate matter at a Pathumthani location, 40 km north of Bangkok, Thailand

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

Oanh, N.T.K.; Reutergardh, L.B.; Dung, N.T.

Total suspended particulate matter in ambient air was sampled by high volume samplers at four sites at the Asian Institute of Technology campus, west of the Phahonyothin Road, Phathumthani Province, 40 km North of Bangkok, Thailand. The concentrations of 18 polycyclic aromatic hydrocarbons (PAHs), were measured by gas liquid chromatography with flame ionization and/or liquid solid chromatography with fluorescence detection. The PAH profile with relatively high concentrations of benzo(ghi)perylene and coronene, decreasing with the distance from the road, suggested a substantial contribution from the traffic. The concentrations in the core of the campus were compatible to those reported for residentialmore » areas in Bangkok, but higher than some western metropolitan areas.« less

High-resolution mid-infrared observations of NGC 7469

NASA Technical Reports Server (NTRS)

Miles, J. W.; Houck, J. R.; Hayward, T. L.

1994-01-01

We present a high-resolution 11.7 micrometer image of the starburst/Seyfert hybrid galaxy NGC 7469 using the Hale 5 m telescope at Palomar Observatory. Our map, with diffraction limited spatial resolution of 0.6 sec, shows a 3 sec diameter ring of emission around an unresolved nucleus. The map is similar to the Very Large Array (VLA) 6 cm map of this galaxy made with 0.4 sec resolution by Wilson et al. (1991). About half of the mid-infrared flux in our map emerges from the unresolved nucleus. We also present spatially resolved low resolution spectra that show that the 11.3 micrometer polycyclic aromatic hydrocarbon (PAH) feature comes from the circumnuclear ring but not from the nucleus of the galaxy.

The determination of polycyclic aromatic hydrocarbons in human urine by high-resolution gas chromatography-mass spectrometry.

PubMed

Cho, Sung-Hee; Lee, Sun-Kyung; Kim, Chong Hyeak

2018-05-01

Polycyclic aromatic hydrocarbons (PAHs), organic compounds formed by at least two condensed aromatic rings, are ubiquitous environmental pollutants that are produced by incomplete combustion of organic materials. PAHs have been classified as carcinogenIC to humans by the International Agency for Research on Cancer, because they can bind to DNA, causing mutations. Therefore, the levels of PAHs in human urine can be used as an indicator for potential carcinogenesis and cell mutation. An analytical method was developed for the accurate measurement of PAHs in urine using high-resolution gas chromatography-mass spectrometry. Urine samples were extracted by an Oasis HLB extraction cartridge after enzymatic hydrolysis with a β-glucuronidase/arylsulfatase cocktail. The 18 PAHs were separated using an Agilent DB-5 MS capillary column (30 m × 0.25 mm, 0.25 μm) and monitored by time-of-flight mass spectrometry. Under the optimized method, the linearity of calibration curves was >0.994. The limits of detection at a signal-to-noise ratio of 3 were 10-100 ng/L. The coefficients of variation were in the range of 0.4-9.0%. The present method was highly accurate for simultaneous determination of 18 PAHs in human urine and could be applied to monitoring and biomedical investigations to check exposure of PAHs. Copyright © 2017 John Wiley & Sons, Ltd.

Polycyclic aromatic hydrocarbons and molecular hydrogen in oxygen-rich planetary nebulae: the case of NGC 6720

PubMed Central

Cox, N. L. J.; Pilleri, P.; Berné, O.; Cernicharo, J.; Joblin, C.

2015-01-01

Evolved stars are primary sources for the formation of polycyclic aromatic hydrocarbons (PAHs) and dust grains. Their circumstellar chemistry is usually designated as either oxygen-rich or carbon-rich, although dual-dust chemistry objects, whose infrared spectra reveal both silicate- and carbon-dust features, are also known. The exact origin and nature of this dual-dust chemistry is not yet understood. Spitzer-IRS mid-infrared spectroscopic imaging of the nearby, oxygen-rich planetary nebula NGC 6720 reveals the presence of the 11.3 μm aromatic (PAH) emission band. It is attributed to emission from neutral PAHs, since no band is observed in the 7–8 μm range. The spatial distribution of PAHs is found to closely follow that of the warm clumpy molecular hydrogen emission. Emission from both neutral PAHs and warm H2 is likely to arise from photo-dissociation regions associated with dense knots that are located within the main ring. The presence of PAHs together with the previously derived high abundance of free carbon (relative to CO) suggest that the local conditions in an oxygen-rich environment can also become conducive to in-situ formation of large carbonaceous molecules, such as PAHs, via a bottom-up chemical pathway. In this scenario, the same stellar source can enrich the interstellar medium with both oxygen-rich dust and large carbonaceous molecules. PMID:26924856

Aromaticity of graphene nanoflakes in a new way: fragment analysis by combination of the nucleus-independent chemical shifts and the anisotropy of current induced density.

PubMed

Li, Qing; Li, Chun-Min; Xu, Hong-Liang; Su, Zhong-Min

2017-08-01

A graphene nanoflake (GNF) is a polycyclic aromatic hydrocarbon (PAH) with a huge two-dimensional π-conjugated carbon material in which a central benzene ring is surrounded by identical benzene-type rings through infinite alternant method. In this paper, we explore the structure-aromaticity relationship of the GNFs and the GNFs with hollow sites (GNFHs) by combining the nucleus-independent chemical shifts (NICS) with the anisotropy of the current induced density (ACID). Firstly, the benzene is a typical aromatic molecule (NICS = -9.671 ppm), GNFs 1-6 is darned with benzene and the corresponding GNFHs 1'-6'. Secondly, the NICS values of GNFs 1-6 alternately vary: -1.214 (1) > -13.847 (2) < -2.662 (3) > -14.530 (4) < -3.932 (5) > -13.978 (6) ppm, the GNFs (2, 4, 6) with even fragments of annulene have larger aromaticity than that of GNFs (1, 3, 5) with odd fragments of annulene. Significantly, the NICS values of GNFs 1-6 can also be fragment analyzed by the NICS values and ACID of benzene and corresponding GNFHs 1'-6'. The NICS values for GNFs (2, 4, 6) can be roughly estimated by the NICS value of benzene minus the NICS value of the GNFHs (2', 4', 6'), respectively. The NICS values for GNFs (1, 3, 5) can be roughly estimated by the NICS value of the GNFHs (1', 3', 5') minus the NICS value of benzene, respectively. We hope that the present work can provide a simple and reliable method for the rational design of the GNF with aromaticity, which may be used to understand the origin of the graphene nanoflake aromatic properties.

Polytetrafluoroethylene-jacketed stirrer modified with graphene oxide and polydopamine for the efficient extraction of polycyclic aromatic hydrocarbons.

PubMed

Zhang, Zinxin; Mwadini, Mwadini Ahmada; Chen, Zilin

2016-10-01

Steel stirrers jacketed with polytetrafluoroethylene can be regarded as an ideal substrate for stirrer bar sorptive extraction. However, it is still a great challenge to immobilize graphene onto a polytetrafluoroethylene stirrer due to the high chemical resistance of the surface of a polytetrafluoroethylene stirrer. We describe here a method to modify the surface of polytetrafluoroethylene stirrers with graphene. In this work, graphene was used as the sorbent due to its excellent adsorption capability for aromatic compounds, such as polycyclic aromatic compounds. Graphene was successfully immobilized onto polytetrafluoroethylene-stirrer by a bio-inspired polydopamine functionalization method. The graphene-modified polytetrafluoroethylene-stirrer shows good stability and tolerance to stirring, ultrasonication, strong acidic and basic solutions, and to organic solvents. The multilayer coating was characterized by scanning electronic microscopy and Fourier transform infrared spectroscopy. After the optimization of some experimental conditions, the graphene-modified polytetrafluoroethylene stirrer was used for the stirrer bar sorptive extraction of polycyclic aromatic hydrocarbons, in which the binding between the polycyclic aromatic hydrocarbons and the graphene layer was mainly based on π-π stacking and hydrophobic interactions. The graphene-modified polytetrafluoroethylene-stirrer-based stirrer bar sorptive extraction and high-performance liquid chromatography method was developed for the determination of polycyclic aromatic hydrocarbons with great extraction efficiency, with enrichment factors from 18 to 62. The method has low limits of detection of 1-5 pg/mL, wide linear range (5-100 and 10-200 pg/mL), good linearity (R ≥ 0.9957) and good reproducibility (RSD ≤ 6.45%). The proposed method has been applied to determine polycyclic aromatic hydrocarbons in real dust samples. Good recoveries were obtained, ranging from 88.53 to 109.43%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

1994-01-01

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

Doped polycyclic aromatic hydrocarbons as building blocks for nanoelectronics: a theoretical study.

PubMed

Dral, Pavlo O; Kivala, Milan; Clark, Timothy

2013-03-01

Density functional theory (DFT) and semiempirical UHF natural orbital configuration interaction (UNO-CI) calculations are used to investigate the effect of heteroatom substitution at the central position of a model polycyclic aromatic hydrocarbon. The effects of the substitution on structure, strain, electronic and spectral properties, and aromaticity of the compounds are discussed.

PAH EXPOSURES OF PRESCHOOL CHILDREN AND THEIR ADULT CAREGIVERS

EPA Science Inventory

The results of four small studies of the polycyclic aromatic hydrocarbon (PAH) exposures of preschool children in low-income families from the Piedmont area of North Carolina were combined to allow comparisons of the total exposures of the children and their adult caregivers. I...

Provisional Guidance for Quantitative Risk Assessment of Polycyclic Aromatic Hydrocarbons

EPA Science Inventory

Polycyclic Aromatic Hydrocarbons (PAHs) are products of incomplete combustion of organic materials; sources are, thus, widespread,including cigarette smoke, municipal waste incineration, wood stove emissions, coal conversion, energy production form fossil fuels, and automobile an...

Infrared Spectra of Polycyclic Aromatic Hydrocarbons (PAHs)

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Bakes, E. L. O.

2000-01-01

We have computed the synthetic infrared spectra of some polycyclic aromatic hydrocarbons containing up to 54 carbon atoms. The species studied include ovalene, circumcoronene, dicoronylene, and hexabenzocoronene. We report spectra for anions, neutrals, cations, and multiply charged cations.

Infrared Spectra of Substituted Polycyclic Aromatic Hydrocarbons

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Hudgins, Douglas M.; Sandford, Scott A.; Allamandola, Louis J.; Arnold, James O. (Technical Monitor)

1997-01-01

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of 1-methylanthracene, 9-methylanthracene, 9-cyanoanthracene, 2-aminoanthracene, acridine, and their positive ions. The theoretical data are compared with matrix-isolation spectra for these species also reported in this work. The theoretical and experimental frequencies and relative intensities for the neutral species are in generally good agreement, whereas the positive ion spectra are only in qualitative agreement. Relative to anthracene, we find that substitution of amethyl or CN for a hydrogen does not significantly affect the spectrum other than to add the characteristic methyl C-H stretch and C-N stretch (near 2200/cm), respectively. However, addition of NH2 dramatically affects the spectrum of the neutral. Not only are the NH2 modes themselves strong, but this electron withdrawing group induces sufficient partial charge on the ring to give the neutral molecule characteristics of the anthracene cation spectrum. The sum of the absolute intensities is about four times larger for 2-aminoanthracene than for 9-cyanoanthracene. Substituting nitrogen in the ring at the nine position (acridine) does not greatly alter the spectrum compared with anthracene.

Synthesis and characterization of a molecularly imprinted polymer for the isolation of the 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) in solution.

PubMed

Ncube, Somandla; Kunene, Phumlile; Tavengwa, Nikita T; Tutu, Hlanganani; Richards, Heidi; Cukrowska, Ewa; Chimuka, Luke

2017-09-01

A smart sorbent consisting of benzo[k]fluoranthene-imprinted and indeno[1 2 3-cd]pyrene-imprinted polymers mixed at 1:1 (w/w) was successfully screened from several cavity-tuning experiments and used in the isolation of polycyclic aromatic hydrocarbons from spiked solution. The polymer mixture showed high cross selectivity and affinity towards all the 16 US-EPA priority polycyclic aromatic hydrocarbons. The average extraction efficiency from a cyclohexane solution was 65 ± 13.3% (n = 16, SD). Batch adsorption and kinetic studies confirmed that the binding of polycyclic aromatic hydrocarbons onto the polymer particles resulted in formation of a monolayer and that the binding process was the rate limiting step. The imprinted polymer performance studies confirmed that the synthesized polymer had an imprinting efficiency of 103.9 ± 3.91% (n = 3, SD). A comparison of the theoretical number of cavities and the experimental binding capacity showed that the overall extent of occupation of the imprinted cavities in the presence of excess polycyclic aromatic hydrocarbons was 128 ± 6.45% (n = 3, SD). The loss of selectivity was estimated at 2.9% with every elution cycle indicating that the polymer can be re-used several times with limited loss of selectivity and sensitivity. The polymer combination has shown to be an effective adsorbent that can be used to isolate all the 16 US-EPA priority polycyclic aromatic hydrocarbons in solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

1993-08-01

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

Occurrence and source apportionment of polycyclic aromatic hydrocarbons in soils and sediment from Hanfeng Lake, Three Gorges, China.

PubMed

Cai, Jing; Gao, Shutao; Zhu, Like; Jia, Xuwei; Zeng, Xiangying; Yu, Zhiqiang

2017-11-10

This study was conducted to investigate the pollutant status and the retention mechanism of polycyclic aromatic hydrocarbons (PAHs) in soils and sediment from bank-water-level-fluctuating zone (WLFZ)-water systems in Hanfeng Lake, Three Gorges, China. The concentrations of the 16 PAHs ranged from 21.8 to 1324 ng g -1 dry wt for all 20 soil and sediment samples. These concentration levels were remarkably lower than those in soils and sediment collected domestically and worldwide. PAHs with two and three rings were found to be dominant in all the samples, with phenanthrene being most abundant. The spatial distribution of PAHs in bank soil, WLFZ soil, and sediment implied that the transfer and fate of PAHs in the bank soil-WLFZ soil-sediment systems were influenced by both water dynamic factors and physicochemical properties of PAHs. Diagnostic ratio analysis and principal component analysis suggested that the PAHs in the areas of Hanfeng Lake were primarily (>75%) derived from coal combustion and vehicle emissions . Use of natural gas, improving gasoline/diesel quality and phasing out old and nonstandard vehicles and ships are proposed to control PAH contamination and protect drinking water safety in the region.

Distribution Characteristics and Risk Assessment of Polycyclic Aromatic Hydrocarbons in the Momoge Wetland, China

PubMed Central

Xu, Jianling; Wang, Hanxi; Sheng, Lianxi; Liu, Xuejun; Zheng, Xiaoxue

2017-01-01

The Momoge Nature Reserve is the research object of this study. Through field sampling, laboratory experiments and analysis, the contents, distribution characteristics, source identification, pollution levels and risk levels of polycyclic aromatic hydrocarbons (PAHs) in wetland soils were studied. The results show that the sum content of 16 types of PAHs (Σ16 PAH) in the wetland soil was within the range (0.029–0.4152) mg/kg. PAHs in wetland soil are primarily 2–3-rings PAHs. PAHs in the Momoge wetland soil have multiple sources: petroleum, combustion of petroleum and coal, and others, of which petroleum and the sum of combustion of petroleum and coal account for 38.0% and 59.3%, respectively. Research, using the standard index and pollution range methods, shows that the content of the PAH labelled Nap, found in the Momoge wetland soil, is excessive; some sampling sites exhibit a low level of pollution. The result of a biotoxicity assessment shows that there are two sampling sites that occasionally present an ecological toxicity hazard. The result of the organic carbon normalization process shows that an ecological risk exists only at sampling site No. 10. PMID:28106776

Assessing risks to adults and preschool children posed by PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) during a biomass burning episode in Northern Thailand.

PubMed

Pongpiachan, Siwatt; Tipmanee, Danai; Khumsup, Chukkapong; Kittikoon, Itthipon; Hirunyatrakul, Phoosak

2015-03-01

To investigate the potential cancer risk resulting from biomass burning, polycyclic aromatic hydrocarbons (PAHs) bound to fine particles (PM2.5) were assessed in nine administrative northern provinces (NNP) of Thailand, before (N-I) and after (N-II) a haze episode. The average values of Σ 3,4-ring PAHs and B[a] P Equivalent concentrations in world urban cities were significantly (p<0.05) much higher than those in samples collected from northern provinces during both sampling periods. Application of diagnostic binary ratios of PAHs underlined the predominant contribution of vehicular exhaust to PM2.5-bound PAH levels in NNP areas, even in the middle of the agricultural waste burning period. The proximity of N-I and N-II values in three-dimensional (3D) principal component analysis (PCA) plots also supports this conclusion. Although the excess cancer risk in NNP areas is much lower than those of other urban area and industrialized cities, there are nevertheless some concerns relating to adverse health impacts on preschool children due to non-dietary exposure to PAHs in home environments. Copyright © 2014 Elsevier B.V. All rights reserved.

Distribution and sources of the polycyclic aromatic hydrocarbons in the sediments of the Pearl River estuary, China.

PubMed

Zhang, Jian-Dong; Wang, You-Shao; Cheng, Hao; Jiang, Zhao-Yu; Sun, Cui-Ci; Wu, Mei-Lin

2015-10-01

The Pearl River delta, one of the most prosperous economically region in China, has experienced significant contaminant inputs. However, the dynamics of pollutants in the Pearl River estuary and the adjacent coastal areas are still unclear at present. In the paper, distribution and sources of polycyclic aromatic hydrocarbons (PAHs) were investigated in the surface sediments of the Pearl River estuary. The total PAHs concentrations ranged from 126.08 to 3828.58 ng/g with a mean value of 563.52 ng/g, whereas the highest PAHs were observed in Guangzhou channel. Among the U.S. Environmental Protection Agency's 16 priority PAHs, PAHs with 3-4 rings exhibited relative higher levels. A positive relationship was found between PAHs and total organic carbon. The source analysis further showed that the major sources of PAHs in the Pearl River estuary were originated from the pyrolytic inputs, reflecting a mixed energy structure such as wood, coal and petroleum combustion. In summary, although PAHs in Lingding Bay and the adjacent coastal areas of the Pearl River estuary exhibited a relatively low pollution level, the relatively high pollution level of PAHs in Guangzhou channel will be attended.

In vivo metabolism and genotoxic effects of nitrated polycyclic aromatic hydrocarbons.

PubMed

Möller, L

1994-10-01

During incomplete combustion of organic matter, nitro-polycyclic aromatic hydrocarbons (nitro-PAHs), are formed in a reaction that is catalyzed by a low pH. 2-Nitrofluorene (NF), a marker for nitro-PAHs, is metabolized in vivo by two different routes. After inhalation, potent mutagenic metabolites, hydroxylated nitrofluorenes (OH-NFs), are formed. The metabolites are distributed by systemic circulation. After oral administration, NF is reduced to the corresponding amine, a reaction mediated by the intestinal microflora. This metabolite is acetylated to 2-acetylaminofluorene (AAF), a potent carcinogen. Further ring-hydroxylation of AAF leads to detoxification and excretion. Induction of cytochrome P450s affects the metabolism, and more OH-NFs are formed. As a consequence, more mutagenic metabolites are found in the circulation. OH-NFs are excreted in the bile as, in terms of mutagenicity, totally harmless glucuronide conjugates. When these conjugates are excreted via the bile, intestinal beta-glucuronidase can liberate direct-acting mutagens in the intestine. Thus, inhalation of NF can lead to formation of potent mutagens in the intestine. NF is a direct-acting mutagen in bacterial assays and an initiator and promoter of the carcinogenic process, and gives rise to DNA adduct formation in laboratory animals.

Spatial-temporal trend and health implications of polycyclic aromatic hydrocarbons (PAHs) in resident oysters, South China Sea: A case study of Eastern Guangdong coast.

PubMed

Yu, Zi-Ling; Lin, Qin; Gu, Yang-Guang; Ke, Chang-Liang; Sun, Run-Xia

2016-09-15

Spatial and temporal distributions of polycyclic aromatic hydrocarbons (PAHs) were investigated in Eastern Guangdong coast, China. Total PAH concentrations in oysters ranged from 231 to 1178ng/g with a mean concentration of 622ng/g dry weight. Compared with other bays and estuaries, PAH levels in oysters were moderate. Spatial distribution of PAHs was site specific, with relatively high PAH concentrations observed in Zhelin Bay and Kaozhouyang Bay. Based on the Spearman test analysis, only PAH concentration in oysters from Jiazi Harbor showed a significant increasing trend (P<0.05). Three-ring PAHs were the most abundant, accounting for 54.2%-88.4% of total PAHs. Diagnostic ratios suggested that PAHs were derived mainly from petroleum origin. BaP and ∑4PAH concentrations were well within the European Union limits (5ng/g and 30ng/g wet weight, respectively). The incremental lifetime cancer risks (ILCR) for PAHs were <10(-5), indicating that the adverse health risks associated with oyster consumption in this area were minimal. Copyright © 2016 Elsevier Ltd. All rights reserved.

On the contribution of polycyclic aromatic hydrocarbons to the carcinogenic impact of automobile exhaust condensate evaluated by local application onto mouse skin.

PubMed

Grimmer, G; Brune, H; Deutsch-Wenzel, R; Naujack, K W; Misfeld, J; Timm, J

1983-11-01

The objective of this investigation was to identify the substances chiefly responsible for the carcinogenicity of automobile exhaust condensate using topical application onto the skin of mice. This was performed by comparing the carcinogenic effect of various fractions with that of an unseparated sample of automobile exhaust condensate, tested in 3 different doses. The probit and Weibull analysis of the result shows: (a) The condensate, emitted from a gasoline-driven automobile provokes local tumors after long-term application to the dorsal skin of mice. The tumor incidence demonstrates a clear cut dose-response relationship. (b) The fraction of polycyclic aromatic hydrocarbons (PAH) containing more than 3 rings accounts for about 84-91% of the total carcinogenicity of automobile exhaust condensate. This fraction represents only about 3.5% by wt of the condensate. (c) The content of benzo[a]pyrene (BaP) (0.414 mg/g) accounts for 6-7.6% of the total carcinogenicity of automobile exhaust condensate, 15 selected PAHs for about 41%. (d) Regarding the minor effect of the PAH-free fraction (about 83% by wt), no hints for a cocarcinogenic activity were observed.

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.

Webinar Presentation: Prenatal Exposures to Polycyclic Aromatic Hydrocarbons (PAH) and Childhood Body Mass Index Trajectories

EPA Pesticide Factsheets

This presentation, Prenatal Exposures to Polycyclic Aromatic Hydrocarbons (PAH) and Childhood Body Mass Index Trajectories, was given at the NIEHS/EPA Children's Centers 2015 Webinar Series held on Feb. 11, 2015.

PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS IN COASTAL GREAT LAKES WATERS

EPA Science Inventory

Photoinduced toxicity is the exacerbated toxicity of environmental contaminants by UV radiation. Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) has been well established in the laboratory for numerous aquatic species including larval fish. The contaminants sub-p...

The influence of sunlight and oxidative treatment on measured PAH concentrations in biochar.

PubMed

Khalid, Fathima N M; Klarup, Doug

2015-09-01

The concentration changes of 18 different polycyclic aromatic hydrocarbons (PAHs) in two different biochars were assessed after (1) chemical oxidative treatment with a solution of H2O2 and Na2S2O8, (2) exposure to sunlight with intermittent wetting, and (3) exposure to sunlight with intermittent wetting after mixing in ZnO and Na2S2O8. Chemical oxidative treatment of biochars derived from gasified wood biochar and a gasified wood/Arundo donax mixture led to decreases in six-ring PAHs, but overall significant increases in measured PAH concentration sums for both biochars (from 225 ± 7 to 312 ± 18 μg g(-1) for wood-derived and 165 ± 3 to 244 ± 7 μg g(-1) for mixture-derived). Sunlight exposure of the mixture-derived biochar led to increases in some three- and four-ring PAHs, but overall decreases in summed PAH concentrations (165 ± 3 to 60 ± 1 μg g(-1) with wetting only and 165 ± 3 to 41 ± 4 μg g(-1) when Na2S2O8 and ZnO were included). The mass losses in the sunlight-exposed samples primarily were due to losses of low molar mass (two-ring) PAHs, though high molar mass (five- and six-ring) PAH concentrations also decreased. This result implies sun and rain exposure to biochar, prior to agricultural application, will help reduce potential PAH soil contamination from the biochar.

Characteristics of polycyclic aromatic hydrocarbons and their gas/particle partitioning from fugitive emissions in coke plants

NASA Astrophysics Data System (ADS)

Mu, Ling; Peng, Lin; Liu, Xiaofeng; Song, Chongfang; Bai, Huiling; Zhang, Jianqiang; Hu, Dongmei; He, Qiusheng; Li, Fan

2014-02-01

Coking is one of the most important emission sources of polycyclic aromatic hydrocarbons (PAHs) in China. However, there is little information available on the emission characteristics of PAHs from fugitive emission during coking, especially on the specific processes dominating the gas-particle partitioning of PAHs. In this study, emission characteristics and gas-particle partitioning of PAHs from fugitive emission in four typical coke plants (CPs) with different scales and techniques were investigated. The average concentrations of total PAHs from fugitive emission at CP2, CP3 and CP4 (stamp charging) were 146.98, 31.82, and 35.20 μg m-3, which were 13.38-, 2.90- and 3.20-fold higher, respectively, than those at CP1 (top charging, 10.98 μg m-3). Low molecular weight PAHs with 2-3 rings made up 75.3% of the total PAHs on average, and the contributions of particulate PAH to the total BaP equivalent concentrations (BaPeq) in each plant were significantly higher than the corresponding contributions to the total PAH mass concentrations. The calculated total BaPeq concentrations varied from 0.19 to 10.86 μg m-3 with an average of 3.14 μg m-3, and more efficient measures to control fugitive emission in coke plants should be employed to prevent or reduce the health risk to workers. Absorption into organic matter dominated the gas-particle partitioning for most of the PAHs including PhA, FluA, Chr, BbF, BkF and BaP, while adsorption on elemental carbon appeared to play a dominant role for AcPy, AcP and Flu.

Identification and removal of polycyclic aromatic hydrocarbons in wastewater treatment processes from coke production plants.

PubMed

Zhang, Wanhui; Wei, Chaohai; Yan, Bo; Feng, Chunhua; Zhao, Guobao; Lin, Chong; Yuan, Mengyang; Wu, Chaofei; Ren, Yuan; Hu, Yun

2013-09-01

Identification and removal of polycyclic aromatic hydrocarbons (PAHs) were investigated at two coke plants located in Shaoguan, Guangdong Province of China. Samples of raw coking wastewaters and wastewaters from subunits of a coke production plant were analyzed using gas chromatography-mass spectrometry (GC/MS) to provide a detailed chemical characterization of PAHs. The identification and characterization of PAH isomers was based on a positive match of mass spectral data of sample peaks with those for PAH isomers in mass spectra databases with electron impact ionization mass spectra and retention times of internal reference compounds. In total, 270 PAH compounds including numerous nitrogen, oxygen, and sulfur heteroatomic derivatives were positively identified for the first time. Quantitative analysis of target PAHs revealed that total PAH concentrations in coking wastewaters were in the range of 98.5 ± 8.9 to 216 ± 20.2 μg/L, with 3-4-ring PAHs as dominant compounds. Calculation of daily PAH output from four plant subunits indicated that PAHs in the coking wastewater came mainly from ammonia stripping wastewater. Coking wastewater treatment processes played an important role in removing PAHs in coking wastewater, successfully removing 92 % of the target compounds. However, 69 weakly polar compounds, including PAH isomers, were still discharged in the final effluent, producing 8.8 ± 2.7 to 31.9 ± 6.8 g/day of PAHs with potential toxicity to environmental waters. The study of coking wastewater herein proposed can be used to better predict improvement of coke production facilities and treatment conditions according to the identification and removal of PAHs in the coke plant as well as to assess risks associated with continuous discharge of these contaminants to receiving waters.

Size distribution and clothing-air partitioning of polycyclic aromatic hydrocarbons generated by barbecue.

PubMed

Lao, Jia-Yong; Wu, Chen-Chou; Bao, Lian-Jun; Liu, Liang-Ying; Shi, Lei; Zeng, Eddy Y

2018-10-15

Barbecue (BBQ) is one of the most popular cooking activities with charcoal worldwide and produces abundant polycyclic aromatic hydrocarbons (PAHs) and particulate matter. Size distribution and clothing-air partitioning of particle-bound PAHs are significant for assessing potential health hazards to humans due to exposure to BBQ fumes, but have not been examined adequately. To address this issue, particle and gaseous samples were collected at 2-m and 10-m distances from a cluster of four BBQ stoves. Personal samplers and cotton clothes were carried by volunteers sitting near the BBQ stoves. Particle-bound PAHs (especially 4-6 rings) derived from BBQ fumes were mostly affiliated with fine particles in the size range of 0.18-1.8 μm. High molecular-weight PAHs were mostly unimodal peaking in fine particles and consequently had small geometric mean diameters and standard deviations. Source diagnostics indicated that particle-bound PAHs in BBQ fumes were generated primarily by combustion of charcoal, fat content in food, and oil. The influences of BBQ fumes on the occurrence of particle-bound PAHs decreased with increasing distance from BBQ stoves, due to increased impacts of ambient sources, especially by petrogenic sources and to a lesser extent by wind speed and direction. Octanol-air and clothing-air partition coefficients of PAHs obtained from personal air samples were significantly correlated to each other. High molecular-weight PAHs had higher area-normalized clothing-air partition coefficients in cotton clothes, i.e., cotton fabrics may be a significant reservoir of higher molecular-weight PAHs. Particle-bound PAHs from barbecue fumes are generated largely from charcoal combustion and food-charred emissions and mainly affiliated with fine particles. Copyright © 2018. Published by Elsevier B.V.

Ecological and health risk-based characterization of agricultural soils contaminated with polycyclic aromatic hydrocarbons in the vicinity of a chemical plant in China.

PubMed

Liu, Geng; Niu, Junjie; Guo, Wenjiong; An, Xiangsheng; Zhao, Long

2016-11-01

Polycyclic aromatic hydrocarbons (PAHs) from chemical plants can cause serious pollution of surrounding agricultural soils. A comprehensive study of agricultural soils was conducted in the vicinity of a chemical plant in China to characterize the soil PAH concentration, as well as their composition and sources. Human health and a screening-level ecological risk assessment were conducted for PAH contamination in agricultural soils. The results showed that the total concentrations of 16 priority PAHs ranged from 250.49 to 9387.26 ng g(-1), with an average of 2780.42 ng g(-1). High molecular weight PAHs (four to six rings) were the dominant component, accounting for more than 60% of all PAHs. Principal component analysis (PCA) and positive matrix factorization model (PMF) suggested that diesel emissions, coal combustion, coke ovens, and fuel combustion and gasoline emissions were the main sources of PAHs in agricultural soils. The ecological risk assessment results based on the effects range-low (ERL), the effects range-median (ERM), and the ecological screening levels (ESL) indicated that the exposure to ∑PAH16 was >ERL, >ERM, and ≥ERL and ESL at 78.1% of the soil sampling stations, and could induce biological effects in mammals. The Bapeq concentrations posed a potential carcinogenic risk to humans. Further risk management and control of soil PAHs in these agricultural soils is required to ensure the safety of the biocoenosis and human health. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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

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

2016-11-01

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

Redox shuttles for overcharge protection of lithium batteries

DOEpatents

Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

2010-12-14

The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

A General Synthetic Route to Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed Annulation Reaction.

PubMed

Shoyama, Kazutaka; Mahl, Magnus; Seifert, Sabine; Würthner, Frank

2018-03-20

Here we report a general method for the synthesis of polycyclic aromatic dicarboximides (PADIs) by palladium-catalyzed annulation of naphthalene dicarboximide to different types of aromatic substrates. Reaction conditions were optimized by systematic variation of ligand, solvent, and additive. It was shown that solvent has a decisive effect on the yield of the reaction products, and thus 1-chloronaphthalene as solvent afforded the highest yield. By applying the optimized reaction conditions, a broad series of planar carbo- and heterocycle containing PADIs were synthesized in up to 97% yield. Moreover, this approach could be applied to curved aromatic scaffold to achieve the respective bowl-shaped PADI. Two-fold annulation was accomplished by employing arene diboronic esters, affording polycyclic aromatic bis(dicarboximides). The optical and electrochemical properties of this broad series of PADIs were explored as well.

ADSORPTION OF POLYCYCLIC AROMATIC HYDROCARBONS IN AGED HARBOR SEDIMENTS

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) are a group of hydrophobic organic contaminants which have low aqueous solubilities and are common pollutants in harbor sediments. Adsorption and desorption isotherms for PAHs are conducted to study the abiotic sorption of PAHs in uncontami...

AGRONOMIC OPTIMIZATION FOR PHYTOREMEDIATION OF POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Phytoremediation is a low-cost method of using plants to degrade, volatilize or sequester organic and metal pollutants that has been used in efforts to remediate sites contaminated with polycyclic aromatic hydrocarbon (PAH) refinery wastes. Non-native plant species aggressivel...

ASSAYING PARTICLE-BOUND POLYCYCLIC AROMATIC HYDROCARBONS (PAH) FROM ARCHIVED PM2.5 FILTERS

EPA Science Inventory

Airborne particulate matter contains numerous organic species, including several polycyclic aromatic hydrocarbons (PAHs) that are known or suspected carcinogens. Existing methods for measuring airborne PAHs are complex and costly, primarily because they are designed to collect...

POLYCYCLIC AROMATIC HYDROCARBON (PAH) EXPOSURE OF 257 PRESCHOOL CHILDREN

EPA Science Inventory

We investigated the polycyclic aromatic hydrocarbon (PAH) exposure of 257 preschool children and their adult caregivers in their everyday environments. Participants were recruited randomly from eligible homes and daycare centers within six North Carolina (NC) and six Ohio (OH) c...

MUTAGENICITY IN SALMONELLA OF SULFUR-CONTAINING POLYCYCLIC AROMATIC HETEROCYCLES AND THEIR DIHYDRODIOL DERIVATIVES

EPA Science Inventory

Polycyclic aromatic sulfur heterocycles (PASH) are common constituents of cigarette smoke, fossil fuel-derived materials, and their combustion byproducts. Many PASH are known mutagens and carcinogens. However, unlike their nonsulfur-containing counterparts, relatively little is k...

Analysis of the impregnation of ZnO:Mn2+ nanoparticles on cigarette filters for trapping polycyclic aromatic hydrocarbons (PAHs)

NASA Astrophysics Data System (ADS)

Estrada-Izquierdo, Irma; Sánchez-Espindola, Esther; Uribe-Hernández, Raúl; Ramón-Gallegos, Eva

2012-10-01

Each cigarette can generate 1149 ng of a mixture of 14 polycyclic aromatic hydrocarbons, of which there are a lot of information about its harmful effects on the environment and human health, they are considered mutagenic, teratogenic and carcinogenic. In this paper we tested ZnO:Mn2+ nanoparticles, attached to the filters of cigarettes. The first results showed that the filtration system was able to catch the Benzo(a)pyrene contained in cigarette smoke; but more tests are needed to quantify the efficiency with greater accuracy over other polycyclic aromatic hydrocarbons.

Conformational Study of Dibenzyl Ether

NASA Astrophysics Data System (ADS)

Hernandez-Castillo, Alicia O.; Abeysekera, Chamara; Hewett, Daniel M.; Zwier, Timothy S.

2017-06-01

Understanding the initial stages of polycyclic aromatic hydrocarbon (PAH) aggregation, the onset of soot formation, is an important goal on the pathway to cleaner combustion processes. PAHs with short alkyl chains, present in fuel-rich combustion environments, can undergo reactions that will chemically link aromatic rings together. One such example of a linked diaryl compound is dibenzyl ether, C_{6}H_{5}-CH_{2}-O-CH_{2}-C_{6}H_{5}. The -CH_{2}-O-CH_{2}- linkage has a length and flexibility well-suited to forming a π-stacked conformation between the two phenyl rings. In this talk, we will explore the single-conformation spectroscopy of dibenzyl ether under jet-cooled conditions in the gas phase. Laser-induced fluorescence, chirped pulse Fourier transform microwave (8-18 GHz region), and single-conformation infrared spectroscopy in the alkyl CH stretch region were all carried out on the molecule, thereby interrogating its full array of electronic, vibrational and rotational degrees of freedom. This work is the first step in a broader study to determine the extent of π-stacking in linked aryl compounds as a function of linkage and PAH size.

Distributions and Sources of Polycyclic Aromatic Hydrocarbons (PAHs) in Soils around a Chemical Plant in Shanxi, China

PubMed Central

Jiao, Haihua; Wang, Qi; Zhao, Nana; Jin, Bo; Zhuang, Xuliang

2017-01-01

Background: Yearly the Shanxi coal chemical industry extracts many coal resources, producing at the same time many polycyclic aromatic hydrocarbons (PAHs) that are emitted as by-products of coal incomplete combustion. Methods: Sixty-six soil samples collected from 0 to 100 cm vertical sections of three different agricultural (AS), roadside (RS) and park (PS) functional soils around a chemical plant in Shanxi, China were analyzed for the presence of the 16 priority control PAHs. Results: The total concentrations (∑16PAHs) varied in a range of 35.4–116 mg/kg, 5.93–66.5 mg/kg and 3.87–76.0 mg/kg for the RS, PS and AS surface soil, respectively, and 5-ring PAHs were found to be dominant (44.4–49.0%), followed by 4-ring PAHs (15.9–24.5%). Moreover, the average value of ∑16PAHs decreased with the depth, 7.87 mg/kg (0–25 cm), 4.29 mg/kg (25–50 cm), 3.00 mg/kg (50–75 cm), 2.64 mg/kg (75–100 cm) respectively, in PS and AS soil vertical sections. Conclusions: The PAH levels in the studied soils were the serious contamination level (over 1.00 mg/kg) according to the Soils Quality Guidelines. The carcinogenic PAHs (ΣBPAHsBapeq) were approximately 14.8 times higher than the standard guideline level (0.60 mg/kg) and 90.3% of PAHs were produced by coal/wood/grass combustion processes. PMID:28991219

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.

Distribution of polycyclic aromatic hydrocarbons in surface water and sediment near a drinking water reservoir in Northeastern China.

PubMed

Liu, Yu; Shen, Jimin; Chen, Zhonglin; Ren, Nanqi; Li, Yifan

2013-04-01

The levels of polycyclic aromatic hydrocarbons (PAHs) in the water and the sediment samples collected near the Mopanshan Reservoir-the most important drinking water resource of Harbin City in Northeast China-were examined. A total of 16 PAHs were concurrently identified and quantified in the three water bodies tested (Lalin River, Mangniu River, and Mopanshan Reservoir) and in the Mopanshan drinking water treatment plant during the high- and low water periods. The total PAH concentrations in the water and sediment samples ranged from 122.7 to 639.8 ng/L and from 89.1 to 749.0 ng/g dry weight, respectively. Similar spatial and temporal trends were also found for both samples. The lowest Σ16PAH concentration of the Mopanshan Reservoir was obtained during the high water period; by contrast, the Lalin River had the highest concentration during the low water period. The PAH profiles resembling the three water bodies, with high percentages of low-molecular weight PAHs and dominated by two- to three-ring PAHs (78.4 to 89.0%). Two of the molecular indices used reflected the possible PAH sources, indicating the main input from coal combustion, especially during the low water period. The conventional drinking water treatment operations resulted in a 20.7 to 67.0% decrease in the different-ringed PAHs in the Mopanshan-treated drinking water. These findings indicate that human activities negatively affect the drinking water resource. Without the obvious removal of the PAHs in the waterworks, drinking water poses certain potential health risks to people.

The sensitive and selective adsorption of aromatic compounds with highly crosslinked polymer nanoparticles

NASA Astrophysics Data System (ADS)

Liu, Shuqin; Chen, Darui; Zheng, Juan; Zeng, Lewei; Jiang, Jijun; Jiang, Ruifeng; Zhu, Fang; Shen, Yong; Wu, Dingcai; Ouyang, Gangfeng

2015-10-01

This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications.This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications. Electronic supplementary information (ESI) available: Fig. S1-S8, details of optimization of the SPME condition, Tables S1-S5. See DOI: 10.1039/c5nr04624f

AMENDMENT OF SEDIMENTS WITH A CARBONACEOUS RESIN REDUCES BIOAVAILABILITY OF POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

A series of laboratory and field test studies were conducted to evaluate the effectiveness of Ambersorb, a carbonaceous resin, in reducing bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated sediments collected from the field. Amending contaminated sediment...

DIGESTIVE BIOAVAILABILITY TO A DEPOSIT FEDDER (ARENICOLA MARINA) OF POLYCYCLIC AROMATIC HYDROCARBONS ASSOCIATED WITH ANTHRPOGENIC PARTICLES

EPA Science Inventory

Marine sediments around urban areas serve as catch basins for anthropogenic particles containing polycyclic aromatic hydrocarbons (PAHs). Using incubations with gut fluids extracted from a deposit-feeding polychaete (Arenicola marina), we determined the digestive bioavailability ...

ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS BY ION TRAP TANDEM MASS SPECTROMETRY

EPA Science Inventory

An ion-trap mass spectrometer with a wave board and tandem mass spectrometry software was used to analyze gas chromatographically separated polycyclic aromatic hydrocarbons (PAHs) by using collision-induced dissociation (CID). The nonresonant (multiple collision) mode was used to...

Susceptibility of eastern oyster early life stages to road surface polycyclic aromatic hydrocarbons (PAHs).

DOT National Transportation Integrated Search

2012-06-01

Polycyclic aromatic hydrocarbons (PAHs) are a class of chemical compounds that are mostly : anthropogenic in nature, and they can become persistent organic contaminants in aquatic : ecosystems. Runoff from impervious surfaces is one of the many ways ...

Identification of persulfate oxidation products of polycyclic aromatic hydrocarbon during remediation of contaminated soil

EPA Science Inventory

The extent of PAH transformation, the formation and transformation of reaction byproducts during persulfate oxidation of polycyclic aromatic hydrocarbons (PAHs) in coking plant soil was investigated. Pre-oxidation analyses indicated that oxygen-containing PAHs (oxy-PAHs) existed ...

COMPUTATIONAL METHODS FOR STUDYING THE INTERACTION BETWEEN POLYCYCLIC AROMATIC HYDROCARBONS AND BIOLOGICAL MACROMOLECULES

EPA Science Inventory

Computational Methods for Studying the Interaction between Polycyclic Aromatic Hydrocarbons and Biological Macromolecules .

The mechanisms for the processes that result in significant biological activity of PAHs depend on the interaction of these molecules or their metabol...

Measurement of gaseous PAHs with an innovative passive sampler in community exposure studies

EPA Science Inventory

A sensitive, simple, and cost-effective passive sampling methodology was developed to quantify gaseous polycyclic aromatic hydrocarbons (PAHs) in personal, indoor and outdoor air. A Fan-Lioy passive PAH sampler (FL-PPS) is constructed from four 80 sections of 1 cm long SPB-5 GC c...

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

Kuo, Li-Jung; Lee, Chon-Lin; Louchouarn, Patrick

A 100-year history of human and natural disturbances in southwestern Taiwan was reconstructed using a suite of molecular markers in four dated sediment cores from the upper slope region off the Gaoping River mouth. Trends in polycyclic aromatic hydrocarbons (PAHs) tracked Taiwan's industrialization/urbanization starting in the 1970s, and the enactment of environmental regulatory policies thereafter.

Profiling Jet Fuel on Neurotoxic Components With Comprehensive Two-Dimensional GC

DTIC Science & Technology

2007-11-01

nitrogen gas to remove possible contaminants that might interfere in the GCxGC-ToF-MS analysis. The generated JP-8 vapor was lead through the...dimension (min) S ec on d di m en si on (s ) Mono Aromatics Polycyclic Aromatic Hydrocarbons Naphthens Sulfur components Alkanes Figure 14...10.0 20.0 30.0 40.0 50.0 60.0 70.0 First dimension (min) S ec on d di m en si on (s ) Mono Aromatics Polycyclic Aromatic Hydrocarbons Naphthens

Cancer Risk Assessment of Polycyclic Aromatic Hydrocarbons in the Soils and Sediments of India: A Meta-Analysis.

PubMed

Tarafdar, Abhrajyoti; Sinha, Alok

2017-10-01

A carcinogenic risk assessment of polycyclic aromatic hydrocarbons in soils and sediments was conducted using the probabilistic approach from a national perspective. Published monitoring data of polycyclic aromatic hydrocarbons present in soils and sediments at different study points across India were collected and converted to their corresponding BaP equivalent concentrations. These BaP equivalent concentrations were used to evaluate comprehensive cancer risk for two different age groups. Monte Carlo simulation and sensitivity analysis were applied to quantify uncertainties of risk estimation. The analysis denotes 90% cancer risk value of 1.770E-5 for children and 3.156E-5 for adults at heavily polluted site soils. Overall carcinogenic risks of polycyclic aromatic hydrocarbons in soils of India were mostly in acceptance limits. However, the food ingestion exposure route for sediments leads them to a highly risked zone. The 90% risk values from sediments are 7.863E-05 for children and 3.999E-04 for adults. Sensitivity analysis reveals exposure duration and relative skin adherence factor for soil as the most influential parameter of the assessment, followed by BaP equivalent concentration of polycyclic aromatic hydrocarbons. For sediments, biota to sediment accumulation factor of fish in terms of BaP is most sensitive on the total outcome, followed by BaP equivalent and exposure duration. Individual exposure route analysis showed dermal contact for soils and food ingestion for sediments as the main exposure pathway. Some specific locations such as surrounding areas of Bhavnagar, Raniganj, Sunderban, Raipur, and Delhi demand potential strategies of carcinogenic risk management and reduction. The current study is probably the first attempt to provide information on the carcinogenic risk of polycyclic aromatic hydrocarbons in soil and sediments across India.

Determination of hydroxylated polycyclic aromatic hydrocarbons by HPLC-photoionization tandem mass spectrometry in wood smoke particles and soil samples.

PubMed

Avagyan, Rozanna; Nyström, Robin; Boman, Christoffer; Westerholm, Roger

2015-06-01

A simple and fast method for analysis of hydroxylated polycyclic aromatic hydrocarbons using pressurized liquid extraction and high performance liquid chromatography utilizing photoionization tandem mass spectrometry was developed. Simultaneous separation and determination of nine hydroxylated polycyclic aromatic hydrocarbons and two hydroxy biphenyls could be performed in negative mode with a run time of 12 min, including equilibration in 5 min. The calibration curves were in two concentration ranges; 1-50 ng/mL and 0.01-50 μg/mL, with coefficients of correlation R (2) > 0.997. The limits of detection and method quantification limits were in the range of 9-56 pg and 5-38 ng/g, respectively. A two-level full factorial experimental design was used for screening of conditions with the highest impact on the extraction. The extraction procedure was automated and suitable for a large number of samples. The extraction recoveries ranged from 70 to 102 % and the matrix effects were between 92 and 104 %. The overall method was demonstrated on wood smoke particles and soil samples with good analytical performance, and five OH-PAHs were determined in the concentration range of 0.19-210 μg/g. As far as we know, hydroxylated polycyclic aromatic hydrocarbons were determined in wood smoke and soil samples using photoionization mass spectrometry for the first time in this present study. Accordingly, this study shows that high performance liquid chromatography photoionization tandem mass spectrometry can be a good option for the determination of hydroxylated polycyclic aromatic hydrocarbons in complex environmental samples. Graphical Abstract The method developed in this study was used to determine hydroxylated polycyclic aromatic hydrocarbons in wood smoke and soil.

Cancer Risk Assessment of Polycyclic Aromatic Hydrocarbons in the Soils and Sediments of India: A Meta-Analysis

NASA Astrophysics Data System (ADS)

Tarafdar, Abhrajyoti; Sinha, Alok

2017-10-01

A carcinogenic risk assessment of polycyclic aromatic hydrocarbons in soils and sediments was conducted using the probabilistic approach from a national perspective. Published monitoring data of polycyclic aromatic hydrocarbons present in soils and sediments at different study points across India were collected and converted to their corresponding BaP equivalent concentrations. These BaP equivalent concentrations were used to evaluate comprehensive cancer risk for two different age groups. Monte Carlo simulation and sensitivity analysis were applied to quantify uncertainties of risk estimation. The analysis denotes 90% cancer risk value of 1.770E-5 for children and 3.156E-5 for adults at heavily polluted site soils. Overall carcinogenic risks of polycyclic aromatic hydrocarbons in soils of India were mostly in acceptance limits. However, the food ingestion exposure route for sediments leads them to a highly risked zone. The 90% risk values from sediments are 7.863E-05 for children and 3.999E-04 for adults. Sensitivity analysis reveals exposure duration and relative skin adherence factor for soil as the most influential parameter of the assessment, followed by BaP equivalent concentration of polycyclic aromatic hydrocarbons. For sediments, biota to sediment accumulation factor of fish in terms of BaP is most sensitive on the total outcome, followed by BaP equivalent and exposure duration. Individual exposure route analysis showed dermal contact for soils and food ingestion for sediments as the main exposure pathway. Some specific locations such as surrounding areas of Bhavnagar, Raniganj, Sunderban, Raipur, and Delhi demand potential strategies of carcinogenic risk management and reduction. The current study is probably the first attempt to provide information on the carcinogenic risk of polycyclic aromatic hydrocarbons in soil and sediments across India.

Fuel quality combustion analysis

NASA Technical Reports Server (NTRS)

Naegeli, D. W.; Moses, C. A.

1979-01-01

A high pressure research combustor operating over a wide range of burner inlet conditions was used to determine the effects of fuel molecular structure on soot formation. Six test fuels with equal hydrogen content (12.8%) were blended to stress different molecular components and final boiling points. The fuels containing high concentrations (20%) of polycyclic aromatics and partially saturated polycyclic structures such as tetralin, produced more soot than would be expected from a hydrogen content correlation for typical petroleum based fuels. Fuels containing naphthenes such as decalin agreed with the hydrogen content correlation. The contribution of polycyclic aromatics to soot formation was equivalent to a reduction in fuel hydrogen content of about one percent. The fuel sensitivity to soot formation due to the polycyclic aromatic contribution decreased as burner inlet pressure and fuel/air ratio increased.

Morphology of Our Galaxy Twin

NASA Image and Video Library

2004-06-28

NASA's Spitzer Space Telescope has captured these infrared images of a nearby spiral galaxy that resembles our own Milky Way. The targeted galaxy, known as NGC 7331 and sometimes referred to as our galaxy's twin, is found in the constellation Pegasus at a distance of 50 million light-years. This inclined galaxy was discovered in 1784 by William Herschel, who also discovered infrared light. The evolution of this galaxy is a story that depends significantly on the amount and distribution of gas and dust, the locations and rates of star formation, and on how the energy from star formation is recycled by the local environment. The new Spitzer images are allowing astronomers to "read" this story by dissecting the galaxy into its separate components. The image, measuring 12.6 by 8.2 arcminutes, was obtained by Spitzer's infrared array camera. It is a four-color composite of invisible light, showing emissions from wavelengths of 3.6 microns (blue), 4.5 microns (green), 5.8 microns (yellow) and 8.0 microns (red). These wavelengths are roughly 10 times longer than those seen by the human eye. The infrared light seen in this image originates from two very different sources. At shorter wavelengths (3.6 to 4.5 microns), the light comes mainly from stars, particularly ones that are older and cooler than our Sun. This starlight fades at longer wavelengths (5.8 to 8.0 microns), where instead we see the glow from clouds of interstellar dust. This dust consists mainly of a variety of carbon-based organic molecules known collectively as polycyclic aromatic hydrocarbons. Wherever these compounds are found, there will also be dust granules and gas, which provide a reservoir of raw materials for future star formation. One feature that stands out in the Spitzer image is the ring of actively forming stars that surrounds the galaxy center (yellow). This ring, with a radius of nearly 20,000 light-years, is invisible at shorter wavelengths, yet has been detected at sub-millimeter and radio wavelengths. It is made up in large part of polycyclic aromatic hydrocarbons. Spitzer measurements suggest that the ring contains enough gas to produce four billion stars like the Sun. Three other galaxies are seen below NGC 7331, all about 10 times farther away. From left to right are NGC 7336, NGC 7335 and NGC 7337. The blue dots scattered throughout the images are foreground stars in the Milky Way; the red ones are galaxies that are even more distant. The Spitzer observations of NGC 7331 are part of a large 500-hour science project, known as the Spitzer Infrared Nearby Galaxy Survey, which will comprehensively study 75 nearby galaxies with infrared imaging and spectroscopy. http://photojournal.jpl.nasa.gov/catalog/PIA06322

Morphology of Our Galaxy's 'Twin'

NASA Technical Reports Server (NTRS)

2004-01-01

NASA's Spitzer Space Telescope has captured these infrared images of a nearby spiral galaxy that resembles our own Milky Way. The targeted galaxy, known as NGC 7331 and sometimes referred to as our galaxy's twin, is found in the constellation Pegasus at a distance of 50 million light-years. This inclined galaxy was discovered in 1784 by William Herschel, who also discovered infrared light.

The evolution of this galaxy is a story that depends significantly on the amount and distribution of gas and dust, the locations and rates of star formation, and on how the energy from star formation is recycled by the local environment. The new Spitzer images are allowing astronomers to 'read' this story by dissecting the galaxy into its separate components.

The image, measuring 12.6 by 8.2 arcminutes, was obtained by Spitzer's infrared array camera. It is a four-color composite of invisible light, showing emissions from wavelengths of 3.6 microns (blue), 4.5 microns (green), 5.8 microns (yellow) and 8.0 microns (red). These wavelengths are roughly 10 times longer than those seen by the human eye.

The infrared light seen in this image originates from two very different sources. At shorter wavelengths (3.6 to 4.5 microns), the light comes mainly from stars, particularly ones that are older and cooler than our Sun. This starlight fades at longer wavelengths (5.8 to 8.0 microns), where instead we see the glow from clouds of interstellar dust. This dust consists mainly of a variety of carbon-based organic molecules known collectively as polycyclic aromatic hydrocarbons. Wherever these compounds are found, there will also be dust granules and gas, which provide a reservoir of raw materials for future star formation.

One feature that stands out in the Spitzer image is the ring of actively forming stars that surrounds the galaxy center (yellow). This ring, with a radius of nearly 20,000 light-years, is invisible at shorter wavelengths, yet has been detected at sub-millimeter and radio wavelengths. It is made up in large part of polycyclic aromatic hydrocarbons. Spitzer measurements suggest that the ring contains enough gas to produce four billion stars like the Sun.

Three other galaxies are seen below NGC 7331, all about 10 times farther away. From left to right are NGC 7336, NGC 7335 and NGC 7337. The blue dots scattered throughout the images are foreground stars in the Milky Way; the red ones are galaxies that are even more distant.

The Spitzer observations of NGC 7331 are part of a large 500-hour science project, known as the Spitzer Infrared Nearby Galaxy Survey, which will comprehensively study 75 nearby galaxies with infrared imaging and spectroscopy.

Formation of Benzene in the Interstellar Medium

NASA Technical Reports Server (NTRS)

Jones, Brant M.; Zhang, Fangtong; Kaiser, Ralf I.; Jamal, Adeel; Mebel, Alexander M.; Cordiner, Martin A.; Charnley, Steven B.; Crim, F. Fleming (Editor)

2010-01-01

Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block-the aromatic benzene molecule-has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3- butadiene, C2H + H2CCHCHCH2 --> C6H6, + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadlene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium.

Formation of benzene in the interstellar medium

PubMed Central

Jones, Brant M.; Zhang, Fangtong; Kaiser, Ralf I.; Jamal, Adeel; Mebel, Alexander M.; Cordiner, Martin A.; Charnley, Steven B.

2011-01-01

Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block—the aromatic benzene molecule—has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3-butadiene, C2H + H2CCHCHCH2 → C6H6 + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadiene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium. PMID:21187430

STUDIES ON BIOREMEDIATION OF POLYCYCLIC AROMATIC HYDROCARBON-CONTAMINATED SEDIMENTS: BIOAVAILABILITY, BIODEGRADABILITY, AND TOXICITY ISSUES

EPA Science Inventory

The widespread contamination of aquatic sediments by polycyclic aromatic hydrocarbons (PAHs) has created a need for cost-effective bioremediation processes, on which the bioavailability and the toxicity of PAHs often have a significant impact. This research investigated the biode...

Webinar Presentation: Exposures to Polycyclic Aromatic Hydrocarbons and Childhood Growth Trajectories and Body Composition: Linkages to Disrupted Self-Regulatory Processes

EPA Pesticide Factsheets

This presentation, Exposures to Polycyclic Aromatic Hydrocarbons and Childhood Growth Trajectories and Body Composition: Linkages to Disrupted Self-Regulatory Processes, was given at the NIEHS/EPA Children's Centers 2016 Webinar Series: Childhood Obesity

Sources and deposition of polycyclic aromatic hydrocarbons to western US national parks

EPA Science Inventory

Seasonal snowpack, lichens, and lake sediment cores were collected from fourteen lake catchments in eight western U.S. National Parks and analyzed for sixteen polycyclic aromatic hydrocarbons (PAHs) to determine their current and historical deposition, as well as to identify thei...

Energy sources of polycyclic aromatic hydrocarbons. [Carcinogenicity of PAHs

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

Guerin, M. R.

1977-01-01

Combustion is the predominant end-process by which fossil fuels are converted to energy. Combustion, particularly when inefficient, is also the primary technological source of polycyclic aromatic hydrocarbons (PAHs) released into the environment. The need for liquid fuels to supply the transportation industry and for nonpolluting fuels for heat and power generation provide the incentive to commercialize processes to convert coal to substitute natural gas and oil. These processes represent a potentially massive new source of environmental PAHs. Insuring an adequate supply of energy with minimum impact on the environment and on health is one of the most important, urgent, andmore » challenging goals currently facing science and technology. Polycyclic aromatic hydrocarbon related carcinogenesis is among the most important of possible occupational- and environmental-health impacts of much of the current and projected national energy base. An understanding of the relationship of polycyclic aromatic hydrocarbons (PAHs) to human cancer and a continued surveillance of energy sources for PAH content are necessary to minimize this impact.« less

Polycyclic aromatic hydrocarbons and heavy metals in the Cispata Bay, Colombia: A marine tropical ecosystem.

PubMed

Burgos-Núñez, Saudith; Navarro-Frómeta, Amado; Marrugo-Negrete, José; Enamorado-Montes, Germán; Urango-Cárdenas, Iván

2017-07-15

The concentrations of polycyclic aromatic hydrocarbons and heavy metals were evaluated in shallow sediments, water, fish and seabird samples from the Cispata Bay, Colombia. The heavy metals concentrations in the sediment was in the following order: Cu>Pb>Hg>Cd. The heavy metal concentration was different (p<0.05) in juvenile and adult birds. High concentrations of mercury were registered in the seabird (10.19±4.99mgkg -1 ) and fish (0.67μgg -1 ) samples. The total concentration of polycyclic aromatic hydrocarbons ranged from 7.0-41ngg -1 in sediment, 0.03-0.34ngmL -1 in water samples, 53.24ngg -1 in fish, and 66ngg -1 in seabirds. The high concentrations of heavy metals in seabirds may be explained by their feeding habits. The presence of polycyclic aromatic hydrocarbons in the Cispata Bay may be due to hydrocarbon spills during oil transport at the nearby oil port. Copyright © 2017 Elsevier Ltd. All rights reserved.

Four faces of the interaction between ions and aromatic rings.

PubMed

Papp, Dóra; Rovó, Petra; Jákli, Imre; Császár, Attila G; Perczel, András

2017-07-15

Non-covalent interactions between ions and aromatic rings play an important role in the stabilization of macromolecular complexes; of particular interest are peptides and proteins containing aromatic side chains (Phe, Trp, and Tyr) interacting with negatively (Asp and Glu) and positively (Arg and Lys) charged amino acid residues. The structures of the ion-aromatic-ring complexes are the result of an interaction between the large quadrupole moment of the ring and the charge of the ion. Four attractive interaction types are proposed to be distinguished based on the position of the ion with respect to the plane of the ring: perpendicular cation-π (CP ⊥ ), co-planar cation-π (CP ∥ ), perpendicular anion-π (AP ⊥ ), and co-planar anion-π (AP ∥ ). To understand more than the basic features of these four interaction types, a systematic, high-level quantum chemical study is performed, using the X -  + C 6 H 6 , M +  + C 6 H 6 , X -  + C 6 F 6 , and M +  + C 6 F 6 model systems with X -  = H - , F - , Cl - , HCOO - , CH 3 COO - and M +  = H + , Li + , Na + , NH4+, CH 3 NH3+, whereby C 6 H 6 and C 6 F 6 represent an electron-rich and an electron-deficient π system, respectively. Benchmark-quality interaction energies with small uncertainties, obtained via the so-called focal-point analysis (FPA) technique, are reported for the four interaction types. The computations reveal that the interactions lead to significant stabilization, and that the interaction energy order, given in kcal mol -1 in parentheses, is CP ⊥ (23-37) > AP ⊥ (14-21) > CP ∥ (9-22) > AP ∥ (6-16). A natural bond orbital analysis performed leads to a deeper qualitative understanding of the four interaction types. To facilitate the future quantum chemical characterization of ion-aromatic-ring interactions in large biomolecules, the performance of three density functional theory methods, B3LYP, BHandHLYP, and M06-2X, is tested against the FPA benchmarks, with the result that the M06-2X functional performs best. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

FISH BILIARY POLYCYCLIC AROMATIC HYDROCARBON METABOLITES ESTIMATED BY FIXED-WAVELENGTH FLUORESCENCE: COMPARISON WITH HPLC-FLUORESCENT DETECTION

EPA Science Inventory

Fixed wavelength fluorescence (FF) was compared to high-performance liquid chromatography with fluorescence detection (HPLC-F) as an estimation of polycyclic aromatic hydrocarbon (PAH) exposure to fish. Two excitation/emission wavelength pairs were used to measure naphthalene- an...

Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

EPA Science Inventory

A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

COMPARISON OF IMMUNOASSAY AND GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR MEASUREMENT OF POLYCYCLIC AROMATIC HYDROCARBONS IN CONTAMINATED SOIL

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) are frequently encountered in the environment and may pose health concerns due to their carcinogenicity. A commercial enzyme-linked immunosorbent assay (ELISA), was evaluated as a screening method for monitoring PAHs at contaminated site...

EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOINDUCED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light received. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

THE EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOACTIVATED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light recieved. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

Polycyclic aromatic hydrocarbons and volatile organic compounds in biochar and biochar-amended soil: A review

USDA-ARS?s Scientific Manuscript database

Residual pollutants including polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), and carbon(aceous) nanoparticles are inevitably generated during the pyrolysis of waste biomass, and remain on the solid co-product called biochar. Such pollutants could have adverse effects on ...

CROSS-INDUCTION OF PYRENE AND PHENANTHRENE IN MYCOBACTERIUM SP. ISOLATED FROM POLYCYCLIC AROMATIC HYDROCARBON CONTAMINATED RIVER SEDIMENTS

EPA Science Inventory

A polycyclic aromatic hydrocarbon (PAH)-degrading culture enriched from contaminated river sediments and a Mycobacterium sp. isolated from the enrichment were tested to investigate the possible synergistic and antagonistic interactions affecting the degradation of pyrene in the p...

Cumulative Exposure Assessment for Trace-Level Polycyclic Aromatic Hydrocarbons (PAHs) using Human Blood and Plasma Analysis

EPA Science Inventory

Humans experience chronic cumulative trace-level exposure to mixtures of volatile, semi-volatile, and non-volatile polycyclic aromatic hydrocarbons (PAHs) present in the environment as by-products of combustion processes. Certain PAHs are known or suspected human carcinogens and ...

Application of sunflower stalk-carbon nitride nanosheets as a green sorbent in the solid-phase extraction of polycyclic aromatic hydrocarbons followed by high-performance liquid chromatography.

PubMed

Marzi Khosrowshahi, Elnaz; Razmi, Habib

2018-02-08

A green biocomposite of sunflower stalks and graphitic carbon nitride nanosheets has been applied as a solid-phase extraction adsorbent for sample preparation of five polycyclic aromatic hydrocarbons in different solutions using high-performance liquid chromatography with ultraviolet detection. Before the modification, sunflower stalks exhibited relatively low adsorption to the polycyclic aromatic hydrocarbons extraction. The modified sunflower stalks showed increased adsorption to the analytes extraction due to the increase in surface and existence of a π-π interaction between the analytes and graphitic carbon nitride nanosheets on the surface. Under the optimal conditions, the limits of detection and quantification for five polycyclic aromatic hydrocarbons compounds could reach 0.4-32 and 1.2-95 ng/L, respectively. The method accuracy was evaluated using recovery measurements in spiked real samples and good recoveries from 71 to 115% with relative standard deviations of <10% have been achieved. The developed method was successfully applied for polycyclic aromatic hydrocarbons determination in various samples-well water, tap water, soil, vegetable, and barbequed meat (kebab)-with analytes contents ranging from 0.065 to 13.3 μg/L. The prepared green composite as a new sorbent has some advantages including ease of preparation, low cost, and good reusability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Procedure for and results of simultaneous determination of aromatic hydrocarbons and fatty acid methyl esters in diesel fuels by high performance liquid chromatography.

PubMed

Kamiński, M; Gilgenast, E; Przyjazny, A; Romanik, G

2006-07-28

The content of aromatic hydrocarbons in diesel fuels is regulated by appropriate standards, and a further reduction in the allowed concentration of these hazardous substances in these fuels is expected. The content of aromatic hydrocarbons in diesel fuels is most often determined using standard methods EN-12916 or ASTM D-6591. The content of polycyclic aromatic hydrocarbons (PAHs) is determined from a single peak obtained using normal phase high-performance liquid chromatography (NP-HPLC), a column of the NH2 type, n-heptane as the eluent, refractive index detector (RID) and backflushing of the eluent. However, the methods mentioned above cannot be applied when the fuel contains fatty acid methyl esters (FAME), which lately has become more common. The content of FAME in diesel oils is determined using mid-IR spectrophotometry based on the absorption of carbonyl group. However, no standard procedure for the determination of classes of aromatic hydrocarbons in diesel fuels containing FAME is yet available. The present work describes such a modification of methods EN-12916/ASTM D-6591 that provides a simultaneous determination of individual groups of aromatic hydrocarbons, total content of polycyclic aromatic hydrocarbons and the FAME content in diesel fuels. The refractive index detector (RID) and n-heptane as the mobile phase are still used, but backflushing of the eluent is applied after the elution of all polycyclic aromatic hydrocarbons. Additionally, ultraviolet diode array detection is used for the exact determination of low contents of polycyclic aromatic hydrocarbons and to confirm the presence of FAME in the analyzed fuel.

Air-sea exchange and gas-particle partitioning of polycyclic aromatic hydrocarbons over the northwestern Pacific Ocean: Role of East Asian continental outflow

NASA Astrophysics Data System (ADS)

Wu, Z.; Guo, Z.

2017-12-01

We measured 15 parent polycyclic aromatic hydrocarbons (PAHs) in atmosphere and water during a research cruise from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) in the spring of 2015 to investigate the occurrence, air-sea gas exchange, and gas-particle partitioning of PAHs with a particular focus on the influence of East Asian continental outflow. The gaseous PAH composition and identification of sources were consistent with PAHs from the upwind area, indicating that the gaseous PAHs (three- to five-ring PAHs) were influenced by upwind land pollution. In addition, air-sea exchange fluxes of gaseous PAHs were estimated to be -54.2 to 107.4 ng m-2 d-1, and was indicative of variations of land-based PAH inputs. The logarithmic gas-particle partition coefficient (logKp) of PAHs regressed linearly against the logarithmic subcooled liquid vapor pressure, with a slope of -0.25. This was significantly larger than the theoretical value (-1), implying disequilibrium between the gaseous and particulate PAHs over the NWP. The non-equilibrium of PAH gas-particle partitioning was shielded from the volatilization of three-ring gaseous PAHs from seawater and lower soot concentrations in particular when the oceanic air masses prevailed. Modeling PAH absorption into organic matter and adsorption onto soot carbon revealed that the status of PAH gas-particle partitioning deviated more from the modeling Kp for oceanic air masses than those for continental air masses, which coincided with higher volatilization of three-ring PAHs and confirmed the influence of air-sea exchange. Meanwhile, significant linear regressions between logKp and logKoa (logKsa) for PAHs were observed for continental air masses, suggesting the dominant effect of East Asian continental outflow on atmospheric PAHs over the NWP during the sampling campaign.

Contamination, source identification, and risk assessment of polycyclic aromatic hydrocarbons in the soils of vegetable greenhouses in Shandong, China.

PubMed

Chai, Chao; Cheng, Qiqi; Wu, Juan; Zeng, Lusheng; Chen, Qinghua; Zhu, Xiangwei; Ma, Dong; Ge, Wei

2017-08-01

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were analyzed in soil (n=196) and vegetable (n=30) collected from greenhouses, and also in the soil (n=27) collected from agriculture fields close to the greenhouses in Shandong Province, China. The total PAH concentration (∑ 16 PAH) ranged from 152.2µg/kg to 1317.7µg/kg, within the moderate range in agricultural soils of China. Three-ring PAHs were the dominant species, with Phe (16.3%), Ace (13.1%), and Fl (10.5%) as the major compounds. The concentrations of low molecular weight (LMW ≤3 rings) PAHs were high in the east and north of Shandong, while the concentrations of high molecular weight (HMW ≥4 rings) PAHs were high in the south and west of the study area. The PAH level in soils in industrial areas (IN) was higher than those in transport areas (TR) and rural areas (RR). No significant difference in concentration of ∑ 16 PAH and composition was observed in soils of vegetable greenhouses and field soils. PAH concentration exhibited a weakly positive correlation with alkaline nitrogen, available phosphorus in soil, but a weakly negative correlation with soil pH. However, no obvious correlation was observed between PAH concentration and organic matter of soil, or ages of vegetable greenhouses. ∑ 16 PAH in vegetables ranged from 89.9µg/kg to 489.4µg/kg, and LMW PAHs in vegetables positively correlated with those in soils. The sources of PAHs were identified and quantitatively assessed through positive matrix factorization. The main source of PAHs in RR was coal combustion, while the source was traffic in TR and IN. Moreover, petroleum source, coke source, biomass combustion, or mixed sources also contributed to PAH pollution. According to Canadian soil quality guidelines, exposure to greenhouse soils in Shandong posed no risk to human health. Copyright © 2017. Published by Elsevier Inc.

Polycyclic aromatic hydrocarbons in surface waters and riverine sediments of the Hooghly and Brahmaputra Rivers in the Eastern and Northeastern India.

PubMed

Khuman, Sanjenbam Nirmala; Chakraborty, Paromita; Cincinelli, Alessandra; Snow, Daniel; Kumar, Bhupander

2018-04-30

Sixteen priority polycyclic aromatic hydrocarbons (PAHs) regulated by the United States Environmental Protection Agency (USEPA) were analyzed in surface waters and riverine sediments of Brahmaputra and Hooghly Rivers, along urban-suburban-rural transects. ∑ 16 PAHs concentrations were higher in Hooghly riverine sediment (HRS) (Avg, 445 ng g -1 ) than Brahmaputra riverine sediment (BRS) (Avg, 169 ng g -1 ) dominated by 4-ring PAHs. In contrast, PAHs concentrations in surface water of Brahmaputra River (BRW) (Avg, 4.04 μg L -1 ) were comparable with Hooghly River (HRW) (Avg, 4.8 μg L -1 ), with dominance by 3-ring PAHs. Toxic PAHs (BaA, Chr, BbF, BkF, BaP, InP and DBA) were dominant in sub-urban transect of HRS (Avg, 387 ng g -1 ) and BRS (Avg, 14 ng g -1 ). Diagnostic ratios, principal component analysis (PCA) and ring wise composition suggested combustion as the main PAHs source in these riverine belts. In BRS, higher PAHs in suburban and rural transects were attributed to incomplete combustion of fossil fuel and biomass burning. In HRS, >85% of high molecular weight PAHs were found in the industrial areas of the suburban transect possibly associated with the discharge of industrial effluents. Harbor and port activities were other major contributors of HMW-PAHs in Hooghly riverine system. Carcinogenic potency estimated in terms of toxic equivalent (TEQ) was several folds higher in HRS (Avg, 106 ng TEQ g -1 ) compared with BRS (Avg, 2.5 ng TEQ g -1 ). Mostly low molecular weight PAHs are likely posing a risk to fishes in both the rivers. Risk on edible fish species may be a matter of concern considering the regular consumption of fishes in this region. Copyright © 2018 Elsevier B.V. All rights reserved.

Air-sea exchange and gas-particle partitioning of polycyclic aromatic hydrocarbons over the northwestern Pacific Ocean: Role of East Asian continental outflow.

PubMed

Wu, Zilan; Lin, Tian; Li, Zhongxia; Jiang, Yuqing; Li, Yuanyuan; Yao, Xiaohong; Gao, Huiwang; Guo, Zhigang

2017-11-01

We measured 15 parent polycyclic aromatic hydrocarbons (PAHs) in atmosphere and water during a research cruise from the East China Sea (ECS) to the northwestern Pacific Ocean (NWP) in the spring of 2015 to investigate the occurrence, air-sea gas exchange, and gas-particle partitioning of PAHs with a particular focus on the influence of East Asian continental outflow. The gaseous PAH composition and identification of sources were consistent with PAHs from the upwind area, indicating that the gaseous PAHs (three-to five-ring PAHs) were influenced by upwind land pollution. In addition, air-sea exchange fluxes of gaseous PAHs were estimated to be -54.2-107.4 ng m -2 d -1 , and was indicative of variations of land-based PAH inputs. The logarithmic gas-particle partition coefficient (logK p ) of PAHs regressed linearly against the logarithmic subcooled liquid vapor pressure (logP L 0 ), with a slope of -0.25. This was significantly larger than the theoretical value (-1), implying disequilibrium between the gaseous and particulate PAHs over the NWP. The non-equilibrium of PAH gas-particle partitioning was shielded from the volatilization of three-ring gaseous PAHs from seawater and lower soot concentrations in particular when the oceanic air masses prevailed. Modeling PAH absorption into organic matter and adsorption onto soot carbon revealed that the status of PAH gas-particle partitioning deviated more from the modeling K p for oceanic air masses than those for continental air masses, which coincided with higher volatilization of three-ring PAHs and confirmed the influence of air-sea exchange. Meanwhile, significant linear regressions between logK p and logK oa (logK sa ) for PAHs were observed for continental air masses, suggesting the dominant effect of East Asian continental outflow on atmospheric PAHs over the NWP during the sampling campaign. Copyright © 2017 Elsevier Ltd. All rights reserved.

PHOTOACTIVATED POLYCYCLIC AROMATIC HYDROCARBON TOXICITY IN MEDAKA (ORYZIAS LATIPES) EMBRYOS: RELEVANCE TO ENVIRONMENTAL RISK IN CONTAMINATED SITES

EPA Science Inventory

The hazard for photoactivated toxicity of polycyclic aromatic hydrocarbons (PAHs) has been clearly demonstrated; however, to our knowledge, the risk in contaminated systems has not been characterized. To address this question, a median lethal dose (LD50) for fluoranthene photoa...

CYCLOPENTA-FUSED POLYCYCLIC AROMATIC HYDROCARBONS IN STRAIN A/J MOUSE LUNG: DNA ADDUCTS, ONCOGENE MUTATIONS, & TUMORIGENESIS

EPA Science Inventory

Cyclopenta-fused Polycyclic Aromatic Hydrocarbons in Strain AJJ Mouse Lung: DNA Adducts, Oncogene Mutations, and Tumorigenesis.

We have examined the relationships between DNA adducts, Ki-ras oncogene mutations, DNA adducts, and adenoma induction in the lungs of strain A/J...

THE APPLICATION OF COMPUTATIONAL MOLECULAR METHODS TO UNDERSTAND THE HEALTH EFFECTS OF ENVIRONMENTAL CHEMICALS-POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

In evaluating the risk posed by chemicals introduced into the environment, information
about their molecular mechanism of action provides a basis for extrapolating from the
laboratory to the environment. Polycyclic aromatic hydrocarbons (PAH) are a large class
of...

POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN OPPOSED FLOW DIFFUSION FLAMES OF ETHANE. (R825412)

EPA Science Inventory

Abstract

The effect of fuel-side carbon density on the levels of polycyclic aromatic hydrocarbon (PAH) formation in atmospheric pressure, opposed flow, ethane diffusion flames has been studied using heated micro-probe sampling and gas chromatography/mass spectrometry (...

IMPORTANCE OF BLACK CARBON IN DISTRIBUTION AND BIOACCUMULATION MODELS OF POLYCYCLIC AROMATIC HYDROCARBONS IN CONTAMINATED MARINE SEDIMENTS

EPA Science Inventory

The roles and relative importance of nonpyrogenic organic carbon (NPOC) and black carbon (BC) as binding phases of polycyclic aromatic hydrocarbons (PAHs) were assessed by their ability to estimate pore water concentrations and biological uptake in various marine sediments. Sedim...

THE PHOTOTOXOICITY OF POLYCYCLIC AROMATIC HYDROCARBONS: A THEORETICAL STUDY OF EXCITED STATES AND CORRELATION TO EXPERIMENT

EPA Science Inventory

Investigators using models to determine the phototoxic effects of sunlight on polycyclic aromatic hydrocarbons (PAHS) have invoked the excited states of the molecule as important in elucidating the mechanism of these reactions. Energies of actual excited states were calcu...

Development of a Relative Potency Factor (Rpf) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures (External Review Draft)

EPA Science Inventory

EPA is conducting a peer review and public comment of the scientific basis supporting the human health hazard and dose-response assessment of polycyclic aromatic hydrocarbon (PAH) mixtures that when finalized will appear on the Integrated Risk Information System (IRIS) database. ...

Particle in a Disk: A Spectroscopic and Computational Laboratory Exercise Studying the Polycyclic Aromatic Hydrocarbon Corannulene

ERIC Educational Resources Information Center

Frey, E. Ramsey; Sygula, Andrzej; Hammer, Nathan I.

2014-01-01

This laboratory exercise introduces undergraduate chemistry majors to the spectroscopic and theoretical study of the polycyclic aromatic hydrocarbon (PAH), corannulene. Students explore the spectroscopic properties of corannulene using UV-vis and Raman vibrational spectroscopies. They compare their experimental results to simulated vibrational…

SOLAR RADIATION DOSE AND PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS: A CASE STUDY

EPA Science Inventory

The toxicity of polycyclic aromatic hydrocarbons increases by as much as three orders of magnitude in the presence of solar radiation. The risk of this photoactive toxicity is thus based on both tissue concentrations of potentially photo activated compounds and the levels of subs...

TRENDS OF POLYCYCLIC AROMATIC HYDROCARBON LEVELS AND MUTAGENICITY IN SANTIAGO'S INHALABLE AIRBORNE PARTICLES IN THE PERIOD 1992-1996.

EPA Science Inventory

Abstract

Trends of polycyclic aromatic hydrocarbons (PAHs) for 1992-1996 (cold season) and their mutagenic activity were investigated in organic extracts from the Santiago. Chile. inhalable particles (PM10). The highest PAH concentrations were observed in 1992 and decline...

POLYCYCLIC AROMATIC HYDROCARBON BIODEGRADATION AS A FUNCTION OF OXYGEN TENSION IN CONTAMINATED SOIL

EPA Science Inventory

Laboratory tests were conducted to determine the effect of soil gas oxygen concentration on the degradation and mineralization of spiked 14C-pyrene and nonspiked 16 priority pollutant polycyclic aromatic hydrocarbons (PAH) present in the soil. The soil used for the evaluation was...

THE RATES OF POLYCYCLIC AROMATIC HYDROCARBON EMISSIONS FROM INCENSE BURNING

EPA Science Inventory

The paper presents the results of experiments performed to determine the amounts of gas- and particle-phase polycyclic aromatic hydrocarbons (PAHS) in incense smoke. Ten brands of incense, 3 of stick, 2 of joss stick, and one each of cone, smudge bundle, rope, powder, and rock, w...

FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)

EPA Science Inventory

The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

75 FR 54628 - Science Advisory Board Staff Office; Notification of a Public Teleconference of the Science...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-09-08

... a Public Teleconference of the Science Advisory Board; Polycyclic Aromatic Hydrocarbon (PAH... Hydrocarbon (PAH) Mixtures Review Panel to discuss its draft report on EPA's Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures. DATES: The SAB PAH Mixtures...

Fluorescence, Absorption, and Excitation Spectra of Polycyclic Aromatic Hydrocarbons as a Tool for Quantitative Analysis

ERIC Educational Resources Information Center

Rivera-Figueroa, A. M.; Ramazan, K. A.; Finlayson-Pitts, B. J.

2004-01-01

A quantitative and qualitative study of the interplay between absorption, fluorescence, and excitation spectra of pollutants called polycyclic aromatic hydrocarbons (PAHs) is conducted. The study of five PAH displays the correlation of the above-mentioned properties along with the associated molecular changes.

ROLE OF SOURCE MATRIX IN THE BIOAVAILABILITY OF POLYCYCLIC AROMATIC HYDROCARBONS TO DEPOSIT-FEEDING BENTHIC INVERTEBRATES

EPA Science Inventory

The bioavailability of polycyclic aromatic hydrocarbons (PAHs) to benthic organisms is complicated by the variety of ways that they are introduced to coastal waters (dissolved, as nonaqueous phase liquids, and tightly bound to soot, coal, tire rubber, and eroded shale). In order ...

Polycyclic Aromatic Hydrocarbons in Fine Particulate Matter Emitted from Burning Kerosene, Liquid Petroleum Gas, and Wood Fuels in Household Cookstoves

EPA Science Inventory

This study measured polycyclic aromatic hydrocarbon (PAH) composition in particulate matter emissions from residential cookstoves. A variety of fuel and cookstove combinations were examined, including: (i) liquid petroleum gas (LPG), (ii) kerosene in a wick stove, (iii) wood (10%...

METHODOLOGY OF AMBIENT AIR MONITORING FOR POLYCYCLIC AROMATIC HYDROCARBONS

EPA Science Inventory

In the last decade, several studies of polycyclic aromatic hydrocarbons (PAH) in ambient air in the U.S. specifically investigated (1) the sampling efficiency of two sorbents for PAH in air: XAD-2 and polyurethane foam (PUP); (2) the storage stability of PAH on quartz fiber fil...

PILOT-SCALE SUBCRITICAL WATER REMEDIATION OF POLYCYCLIC AROMATIC HYDROCARBON- AND PESTICIDE-CONTAMINATED SOIL. (R825394)

EPA Science Inventory

Subcritical water (hot water under enough pressure to maintain the liquid
state) was used to remove polycyclic aromatic hydrocarbons (PAHs) and pesticides
from highly contaminated soils. Laboratory-scale (8 g of soil) experiments were
used to determine conditions f...

Remobilization of polycyclic aromatic hydrocarbons and organic matter in seawater during sediment resuspension experiments from a polluted coastal environment: Insights from Toulon Bay (France).

PubMed

Guigue, Catherine; Tedetti, Marc; Dang, Duc Huy; Mullot, Jean-Ulrich; Garnier, Cédric; Goutx, Madeleine

2017-10-01

Polycyclic aromatic hydrocarbons (PAHs) and organic matter contents were measured in seawater during resuspension experiments using sediments collected from Toulon Bay (Northwestern Mediterranean Sea, France). The studied sediments were very highly contaminated in PAHs, especially in 4-ring compounds emitted from combustion processes. The sediments used for resuspension experiments were collected at 0-2 cm (diagenetically new organic matter, OM) and 30-32 cm depths (diagenetically transformed OM). They were both mostly composed of fine particles (<63 μm), enriched in organic carbon (8.2 and 6.3%, respectively) and in PAHs (concentration of Σ34 PAHs: 38.2 and 35.7 × 10 3  ng g -1 , respectively). The resuspension of these sediments led to an increase in concentrations of dissolved Σ34 PAHs, dissolved organic carbon (DOC) and dissolved humic- and tryptophan-like fluorophores in seawater up to 10-, 1.3-, 4.4- and 5.7-fold, respectively. The remobilization in seawater was higher for 4-6 ring PAHs, especially benzo(g,h,i)perylene, whose concentration exceeded the threshold values of the European Water Framework Directive. This noted the potential harmful effects of sediment resuspension on marine biota. From these sediment resuspension experiments, we determined OC-normalized partition coefficients of PAHs between sediment and water (K oc ) and found that during such events, the transfer of PAHs from sediment particles to seawater was lower than that predicted from octanol-water partition coefficients (K ow ) (i.e., measured K oc  > K oc predicted from K ow ). The results confirmed the sequestration role of sedimentary OC quality and grain size on PAHs; the OM diagenetic state seemed to impact the partition process but in a relatively minor way. Furthermore, differences were observed between 2-4 ring and 5-6 ring PAHs, with the latter displaying a relatively higher mobility towards seawater. These differences may be explained by the distribution of these two PAH pools within different OM moieties, such as humic substances and black carbon. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nitro-polycyclic aromatic hydrocarbons - gas-particle partitioning, mass size distribution, and formation along transport in marine and continental background air

NASA Astrophysics Data System (ADS)

Lammel, Gerhard; Mulder, Marie D.; Shahpoury, Pourya; Kukučka, Petr; Lišková, Hana; Přibylová, Petra; Prokeš, Roman; Wotawa, Gerhard

2017-05-01

Nitro-polycyclic aromatic hydrocarbons (NPAH) are ubiquitous in polluted air but little is known about their abundance in background air. NPAHs were studied at one marine and one continental background site, i.e. a coastal site in the southern Aegean Sea (summer 2012) and a site in the central Great Hungarian Plain (summer 2013), together with the parent compounds, PAHs. A Lagrangian particle dispersion model was used to track air mass history. Based on Lagrangian particle statistics, the urban influence on samples was quantified for the first time as a fractional dose to which the collected volume of air had been exposed. At the remote marine site, the 3-4-ring NPAH (sum of 11 targeted species) concentration was 23.7 pg m-3 while the concentration of 4-ring PAHs (6 species) was 426 pg m-3. The most abundant NPAHs were 2-nitrofluoranthene (2NFLT) and 3-nitrophenanthrene. Urban fractional doses in the range of < 0.002-5.4 % were calculated. At the continental site, the Σ11 3-4-ring NPAH and Σ6 4-ring PAH were 58 and 663 pg m-3, respectively, with 9-nitroanthracene and 2NFLT being the most concentrated amongst the targeted NPAHs. The NPAH levels observed in the marine background air are the lowest ever reported and remarkably lower, by more than 1 order of magnitude, than 1 decade before. Day-night variation of NPAHs at the continental site reflected shorter lifetime during the day, possibly because of photolysis of some NPAHs. The yields of formation of 2NFLT and 2-nitropyrene (2NPYR) in marine air seem to be close to the yields for OH-initiated photochemistry observed in laboratory experiments under high NOx conditions. Good agreement is found for the prediction of NPAH gas-particle partitioning using a multi-phase poly-parameter linear free-energy relationship. Sorption to soot is found to be less significant for gas-particle partitioning of NPAHs than for PAHs. The NPAH levels determined in the south-eastern outflow of Europe confirm intercontinental transport potential.

Polycyclic Aromatic Hydrocarbons in Urban Soil in the Semi-arid City of Xi'an, Northwest China: Composition, Distribution, Sources, and Relationships with Soil Properties.

PubMed

Wang, Lijun; Zhang, Panqing; Wang, Li; Zhang, Wenjuan; Shi, Xingmin; Lu, Xinwei; Li, Xiaoping; Li, Xiaoyun

2018-03-27

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment. This study collected a total of 62 urban soil samples from the typical semi-arid city of Xi'an in Northwest. They were analyzed for the composition, distribution, and sources of PAHs as well as the relationships with soil properties. The sum of 16 individual PAHs (∑16PAHs) ranged from 390.6 to 10,652.8 μg/kg with a mean of 2052.6 μg/kg. The average ∑16PAHs decreased in the order of the third ring road (2321.1 μg/kg) > the first ring road (1893.7 μg/kg) > the second ring road (1610.0 μg/kg), and in the order of industrial areas (3125.6 μg/kg) > traffic areas (2551.6 μg/kg) > educational areas (2414.4 μg/kg) > parks (1649.5 μg/kg) > mixed commercial and traffic areas (1332.8 μg/kg) > residential areas (1031.0 μg/kg). The most abundant PAHs in the urban soil were 3- to 5-ring PAHs. Elevated levels of PAHs were found in industrial and traffic areas from the east and west suburbs and the northwest corner of Xi'an as well as the northeast corner in the urban district of Xi'an. PAHs in the urban soil were mainly related to the combustion of fossil fuel (i.e., coal, gasoline, diesel, and natural gas) and biomass (i.e., grass and wood) (variance contribution 57.2%) as well as the emissions of petroleum and its products (variance contribution 29.9%). Soil texture and magnetic susceptibility were the main factors affecting the concentration of PAHs in urban soil. Meanwhile, this study suggested that the single, rapid, and nondeductive magnetic measurements can be an indicator of soil pollution by PAHs.

SYNCHRONOUS FLUOROMETRIC MEASUREMENT OF METABOLITES OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE BILE OF BROWN BULLHEAD

EPA Science Inventory

A synchronous fluorescent spectroscopy (SFS) method was developed to measure pyrene-type metabolites in the bile of brown bullhead (Ameiurus nebulosus) and to estimate the exposure of fish to PAHs in four Lake Erie tributaries collected in the spring and fall of 1990 and 1991. Fo...

Chemical characterization of biomass fuel particulate deposits and ashes in households of Mt. Everest region (NEPAL).

PubMed

Ielpo, Pierina; Fermo, Paola; Comite, Valeria; Mastroianni, Domenico; Viviano, Gaetano; Salerno, Franco; Tartari, Gianni

2016-12-15

During a sampling campaign, carried out during June 2012, inside some traditional households located in four villages (Phakding, Namche, Pangboche and Tukla) of Mt. Everest region in southern part of the central Himalaya (Nepal), particulate matter (PM) depositions and ashes have been collected. Moreover, outdoor PM depositions have also been analyzed. Chemical characterization of PM depositions and ashes for major ions, organic carbon, elemental carbon (EC), metal content and PAHs (Polycyclic Aromatic Hydrocarbons) allowed identifying, as major contributes to indoor PM, the following sources: biomass burning, cooking and chimney ashes. These sources significantly affect outdoor PM depositions: in-house biomass burning is the major source for outdoor EC and K + as well as biomass burning and cooking activities are the major sources for Polycyclic Aromatic Hydrocarbons. Copyright © 2016 Elsevier B.V. All rights reserved.

Identification and characterization of epoxide hydrolase activity of polycyclic aromatic hydrocarbon-degrading bacteria for biocatalytic resolution of racemic styrene oxide and styrene oxide derivatives.

PubMed

Woo, Jung-Hee; Kwon, Tae-Hyung; Kim, Jun-Tae; Kim, Choong-Gon; Lee, Eun Yeol

2013-04-01

A novel epoxide hydrolase (EHase) from polycyclic aromatic hydrocarbon (PAH)-degrading bacteria was identified and characterized. EHase activity was identified in four strains of PAH-degrading bacteria isolated from commercial gasoline and oil-contaminated sediment based on their growth on styrene oxide and its derivatives, such as 2,3- and 4-chlorostyrene oxides, as a sole carbon source. Gordonia sp. H37 exhibited high enantioselective hydrolysis activity for 4-chlorostyrene oxide with an enantiomeric ratio of 27. Gordonia sp. H37 preferentially hydrolyzed the (R)-enantiomer of styrene oxide derivatives resulting in the preparation of a (S)-enantiomer with enantiomeric excess greater than 99.9 %. The enantioselective EHase activity was identified and characterized in various PAH-degrading bacteria, and whole cell Gordonia sp. H37 was employed as a biocatalyst for preparing enantiopure (S)-styrene oxide derivatives.

Polycyclic aromatic hydrocarbon optical properties and contribution to the acceleration of stellar outflows

NASA Technical Reports Server (NTRS)

Cherchneff, Isabelle; Barker, John R.; Tielens, Alexander G. G. M.

1991-01-01

The optical constants of four polycyclic aromatic hydrocarbon (PAH) molecules (benzene, pyrene, pentacene, and coronene) are determined from their measured laboratory absorption spectra. The Planck mean of the radiation pressure cross section is computed for each molecule and for amorphous carbon (AC) grains, and semiempirically estimated for large PAH molecules up to 400 carbon atoms. Assuming that PAHs are present in carbon-rich stellar outflows, the radiation pressure forces acting on them are calculated and compared with the radiation forces on AC particles. The results show that PAHs possess very different optical properties from AC grains. Small PAHs may experience an 'inverse greenhouse' effect in the inner part of the envelope, as they decouple from the gas close to the photosphere. The radiation pressure force on PAHs is always much less than the force at work on AC grains, and PAH molecules do not affect significantly the dynamics of the outflow.

Towards the Rational Design of Ionic Liquid Matrices for Secondary Ion Mass Spectrometry: Role of the Anion

NASA Astrophysics Data System (ADS)

Dertinger, Jennifer J.; Walker, Amy V.

2013-08-01

The role of the ionic liquid (IL) anion structure on analyte signal enhancements has been systematically investigated in secondary ion mass spectrometry (SIMS) using a variety of samples, including lipids, sterols, polymers, and peptides. Twenty-four ILs were synthesized. The 12 matrix acids were cinnamic acid derivatives. Two bases were employed: 1-methylimidazole and tripropylamine. Three matrices, methylimmidazolium o-coumarate, tripropylammonium o-coumarate, and tripropylammonium 3,4,5-trimethoxycinnamate, were "universal" matrices enhancing all analytes tested. The pKa of the matrix acid does not appear to have a strong effect on analyte ion intensities. Rather, it is observed that a single hydroxyl group on the anion aromatic ring leads to significantly increased molecular ion intensities. No analyte signal enhancements were observed for -CH3, -CF3 and -OCH3 groups present on the aromatic ring. The position of the -OH group on the aromatic ring also alters molecular ion intensity enhancements. As well as the chemical identity and position of substituents, the number of moieties on the aromatic ring may affect the analyte signal enhancements observed. These observations suggest that the activation of the IL anion aromatic ring is important for optimizing analyte signal intensities. The implications for SIMS imaging of complex structures, such as biological samples, are discussed.

Microbial diversity and activity of an aged soil contaminated by polycyclic aromatic hydrocarbons.

PubMed

Zhao, Xiaohui; Fan, Fuqiang; Zhou, Huaidong; Zhang, Panwei; Zhao, Gaofeng

2018-06-01

In-depth understanding of indigenous microbial assemblages resulted from aged contamination by polycyclic aromatic hydrocarbons (PAHs) is of vital importance in successful in situ bioremediation treatments. Soil samples of three boreholes were collected at 12 different vertical depths. Overall, the dominating three-ring PAHs (76.2%) were closely related to distribution patterns of soil dehydrogenase activity, microbial cell numbers, and Shannon biodiversity index (H') of indigenous microorganisms. High-molecular-weight PAHs tend to yield more diverse communities. Results from 16S rRNA analysis indicated that possible functional groups of PAH degradation include three species in Bacillus cereus group, Bacillus sp. SA Ant14, Nocardioides sp., and Ralstonia pickettii. Principal component analysis indicates significant positive correlations between the content of high-molecular-weight PAHs and the distribution of Bacillus weihenstephanensis KBAB4 and Nocardioides sp. The species B. cereus 03BB102, Bacillus thuringiensis, B. weihenstephanensis KBAB4, and Nocardioides sp. were recognized as main PAH degraders and thus recommended to be utilized in further bioremediation applications. The vertical distribution characteristics of PAHs in soil profiles (1-12 m) and the internal relationship between the transport mechanisms of PAHs and the response of soil biological properties help further understand the microbial diversity and activity in an aged site.

Quantitative assessment of human health risk posed by polycyclic aromatic hydrocarbons in urban road dust.

PubMed

Ma, Yukun; Liu, An; Egodawatta, Prasanna; McGree, James; Goonetilleke, Ashantha

2017-01-01

Among the numerous pollutants present in urban road dust, polycyclic aromatic hydrocarbons (PAHs) are among the most toxic chemical pollutants and can pose cancer risk to humans. The primary aim of the study was to develop a quantitative model to assess the cancer risk from PAHs in urban road dust based on traffic and land use factors and thereby to characterise the risk posed by PAHs in fine (<150μm) and coarse (>150μm) particles. The risk posed by PAHs was quantified as incremental lifetime cancer risk (ILCR), which was modelled as a function of traffic volume and percentages of different urban land uses. The study outcomes highlighted the fact that cancer risk from PAHs in urban road dust is primarily influenced by PAHs associated with fine solids. Heavy PAHs with 5 to 6 benzene rings, especially dibenzo[a,h]anthracene (D[a]A) and benzo[a]pyrene (B[a]P) in the mixture contribute most to the risk. The quantitative model developed based on traffic and land use factors will contribute to informed decision making in relation to the management of risk posed by PAHs in urban road dust. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of central ventilation and air conditioner system on the concentration and health risk from airborne polycyclic aromatic hydrocarbons.

PubMed

Lv, Jinze; Zhu, Lizhong

2013-03-01

Central ventilation and air conditioner systems are widely utilized nowadays in public places for air exchange and temperature control, which significantly influences the transfer of pollutants between indoors and outdoors. To study the effect of central ventilation and air conditioner systems on the concentration and health risk from airborne pollutants, a spatial and temporal survey was carried out using polycyclic aromatic hydrocarbons (PAHs) as agent pollutants. During the period when the central ventilation system operated without air conditioning (AC-off period), concentrations of 2-4 ring PAHs in the model supermarket were dominated by outdoor levels, due to the good linearity between indoor air and outdoor air (r(p) > 0.769, p < 0.05), and the slopes (1.2-4.54) indicated that ventilating like the model supermarket increased the potential health risks from low molecular weight PAHs. During the period when the central ventilation and air conditioner systems were working simultaneously (AC-on period), although the total levels of PAHs were increased, the concentrations and percentage of the particulate PAHs indoors declined significantly. The BaP equivalency (BaPeq) concentration indicated that utilization of air conditioning reduced the health risks from PAHs in the model supermarket.

Bioavailability of Carbon Nanomaterial-Adsorbed Polycyclic Aromatic Hydrocarbons to Pimphales promelas: Influence of Adsorbate Molecular Size and Configuration.

PubMed

Linard, Erica N; Apul, Onur G; Karanfil, Tanju; van den Hurk, Peter; Klaine, Stephen J

2017-08-15

Despite carbon nanomaterials' (CNMs) potential to alter the bioavailability of adsorbed contaminants, information characterizing the relationship between adsorption behavior and bioavailability of CNM-adsorbed contaminants is still limited. To investigate the influence of CNM morphology and organic contaminant (OC) physicochemical properties on this relationship, adsorption isotherms were generated for a suite of polycyclic aromatic hydrocarbons (PAHs) on multiwalled carbon nanotubes (MWCNTs) and exfoliated graphene (GN) in conjunction with determining the bioavailability of the adsorbed PAHs to Pimphales promelas using bile analysis via fluorescence spectroscopy. Although it appeared that GN adsorbed PAHs indiscriminately compared to MWCNTs, the subsequent bioavailability of GN-adsorbed PAHs was more sensitive to PAH morphology than MWCNTs. GN was effective at reducing bioavailability of linear PAHs by ∼70%, but had little impact on angular PAHs. MWCNTs were sensitive to molecular size, where bioavailability of two-ringed naphthalene was reduced by ∼80%, while bioavailability of the larger PAHs was reduced by less than 50%. Furthermore, the reduction in bioavailability of CNM-adsorbed PAHs was negatively correlated with the amount of CNM surface area covered by the adsorbed-PAHs. This study shows that the variability in bioavailability of CNM-adsorbed PAHs is largely driven by PAH size, configuration and surface area coverage.

[Pollution characteristics and sources of polycyclic aromatic hydrocarbons in riparian soils along urban rivers of Wenzhou city].

PubMed

Zhou, Jie-Cheng; Bi, Chun-Juan; Chen, Zhen-Lou; Wang, Lu; Xu, Shi-Yuan; Pan, Qi

2012-12-01

Twenty one riparian soil samples along Jiushanwai River and Shanxia River of Wenzhou city were collected in August 2010 to investigate the pollution characteristics of polycyclic aromatic hydrocarbons (PAHs). The samples were extracted by an accelerated solvent extractor (ASE), purified by a purification column and determined by GC-MS. Results showed that the total concentrations of PAHs in the riparian soils ranged from 60.7 ng x g(-1) to 3 871.3 ng x g(-1), and the concentrations of sigma PAHs in soils along the Shanxia River were significantly lower than the levels along Jiushanwai River. The dominant compounds were 2 to 3 rings in the riparian soils along both rivers, which in average accounted for 62.47% - 72.51% in sigma PAHs. Compared with the PAHs concentrations in soils of other areas in the world, the riparian soils of the studied rivers were moderately polluted by PAHs, but the concentrations of BaP in three soil samples were much higher than the soil standard value of the former Soviet Union, which should be paid more attention. Based on the ratios of Ant/(Ant + Phe) and Fla/(Fla + Pyr) and principal component analysis results, PAHs in riparian soils of the studied rivers were mainly derived from both the petroleum and combustion.

Removal of polycyclic aromatic hydrocarbons (PAHs) from industrial sludges in the ambient air conditions: automotive industry.

PubMed

Karaca, Gizem; Tasdemir, Yucel

2013-01-01

Removal of polycyclic aromatic hydrocarbons (PAHs) existed in automotive industry treatment sludge was examined by considering the effects of temperature, UV, titanium dioxide (TiO2) and diethyl amine (DEA) in different dosages (i.e., 5% and 20%) in this study. Application of TiO2 and DEA to the sludge samples in ambient environment was studied. Ten PAH (Σ10 PAH) compounds were targeted and their average value in the sludge was found to be 4480 ± 1450 ng/g dry matter (DM). Total PAH content of the sludge was reduced by 25% in the ambient air environment. Meteorological conditions, atmospheric deposition, evaporation and sunlight irradiation played an effective role in the variations in PAH levels during the tests carried out in ambient air environment. Moreover, it was observed that when the ring numbers of PAHs increased, their removal rates also increased. Total PAH level did not change with the addition of 5% DEA and only 10% decreased with 5% TiO2 addition. PAH removal ratios were 8% and 32% when DEA (20%) and TiO2 (20%) were added, respectively. It was concluded that DEA was a weak photo-sensitizer yet TiO2 was effective only at 20% dosage.

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.

Bioremediation of PAH-contamined soils: Consequences on formation and degradation of polar-polycyclic aromatic compounds and microbial community abundance.

PubMed

Biache, Coralie; Ouali, Salma; Cébron, Aurélie; Lorgeoux, Catherine; Colombano, Stéfan; Faure, Pierre

2017-05-05

A bioslurry batch experiment was carried out over five months on three polycyclic aromatic compound (PAC) contaminated soils to study the PAC (PAH and polar-PAC) behavior during soil incubation and to evaluate the impact of PAC contamination on the abundance of microbial communities and functional PAH-degrading populations. Organic matter characteristics and reactivity, assessed through solvent extractable organic matter and PAC contents, and soil organic matter mineralization were monitored during 5 months. Total bacteria and fungi, and PAH-ring hydroxylating dioxygenase genes were quantified. Results showed that PAHs and polar-PACs were degraded with different degradation dynamics. Differences in degradation rates were observed among the three soils depending on PAH distribution and availability. Overall, low molecular weight compounds were preferentially degraded. Degradation selectivity between isomers and structurally similar compounds was observed which could be used to check the efficiency of bioremediation processes. Bacterial communities were dominant over fungi and were most likely responsible for PAC degradation. Abundance of PAH-degrading bacteria increased during incubations, but their proportion in the bacterial communities tended to decrease. The accumulation of some oxygenated-PACs during the bioslurry experiment underlines the necessity to monitor these compounds during application of remediation treatment on PAH contaminated soils. Copyright © 2017 Elsevier B.V. All rights reserved.

DEPENDENCY OF POLYCHLORINATED BIPHENYL AND POLYCYCLIC AROMATIC HYDROCARBON BIOACCUMULATION IN MYA ARENARIA ON BOTH WATER COLUMN AND SEDIMENT BED CHEMICAL ACTIVITIES

EPA Science Inventory

The bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by the filter-feeding soft-shell clam Mya arenaria was evaluated at three sites near Boston (MA, USA) by assessing the chemical activities of those hydrophobic organic compounds (H...

REAL-TIME AND INTEGRATED MEASUREMENT OF POTENTIAL HUMAN EXPOSURE TO PARTICLE-BOUND POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) FROM AIRCRAFT EXHAUST

EPA Science Inventory

Real-time monitors and low-volume air samplers were used to measure the potential human exposure to airborne polycyclic aromatic hydrocarbon (PAH) concentrations during various flight-related and ground-support activities of C-130H aircraft at an Air National Guard base. Three...

Role of sooty mold fungi in degradation of polycycllic aromatic hydrocarbons (PAHS) in soil

Treesearch

Venera A. Jouraeva; David L. Johnson; John P. Hassett; David J. Nowak; Natalia A. Shipunova; Dana Barbarossa

2006-01-01

The focus of this research was on elucidation of the role of deciduous tree ecosystems in accumulation of fine-particle-associated polycyclic aromatic hydrocarbons (PAHs) and heavy metals on leaves of deciduous trees. The studied species were Tilia x euchlora (frequently infested by sooty mold fungi) and Pyrus calleryana (...

The Influence of Multiwalled Carbon Nanotubes on Polycyclic Aromatic Hydrocarbon (PAH) Bioavailability and Toxicity to Soil Microbial Communities in Alfalfa Rhizosphere

USDA-ARS?s Scientific Manuscript database

Carbon nanotubes (CNTs) may affect bioavailability and toxicity of organic contaminants due to their adsorption properties. Recent studies have observed the influence of multiwalled carbon nanotubes (MWNTs) on the fate of polycyclic aromatic hydrocarbons (PAHs) and other organic contaminants. Greenh...

Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures (Interagency Science Consultation Draft)

EPA Science Inventory

On February 26, 2010, the draft Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures document and the charge to external peer reviewers were released for external peer review and public comment. The draft document and t...

RELATING DAILY SOLAR ULTRAVIOLET RADIATION DOSE IN SALT MARSH-ASSOCIATED ESTUARINE SYSTEMS TO LABORATORY ASSESSMENTS OF PHOTOACTIVATED POLYCYCLIC AROMATIC HYDROCARBON TOXICITY

EPA Science Inventory

Estuaries of the southeastern United States not only serve an important nursery function but also are common repositories of polycyclic aromatic hydrocarbons (PAHs) derived from upland activities. Thus, these habitats may be at risk for PAHphototoxicity. To better characterize ...

SEASONAL VARIATION OF THE PARTICLE SIZE DISTRIBUTION OF POLYCYCLIC AROMATIC HYDROCARBONS AND OF MAJOR AEROSOL SPECIES IN CLAREMONT, CALIFORNIA. (R827352C020)

EPA Science Inventory

As part of the Southern California Particle Center and Supersite (SCPCS) activities, we measured, during all seasons, particle size distributions of 12 priority pollutant polycyclic aromatic hydrocarbons (PAHs), concurrently with elemental carbon (EC), organic carbon (OC), sul...

Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants....mass spectrometry

USDA-ARS?s Scientific Manuscript database

A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated...

A COMPUTER DOCKING STUDY OF THE BINDING OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR METABOLITES TO THE LIGARD-BINDING DOMAIN OF THE ESTROGEN RECEPTOR

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) are a class of ubiquitous, anthropogenic chemicals found in the environment. In the present study, computational methods are used to evaluate their potential estrogenicity and the contribution chemicals in this class make to environmental e...

WHY DOES 5-METHYL CHRYSENE INTERACT WITH DNA LIKE BOTH A PLANAR AND A NON-PLANAR POLYCYCLIC AROMATIC HYDROCARBON? QUANTUM MECHANICAL STUDIES

EPA Science Inventory

Polycyclic aromatic hydrocarbons are a large class of anthropogenic chemicals found in the environment. Some class members are potent animal carcinogens while other similar class members show little carcinogenic activity. When considering a series of in vitro studies of the int...

PHOTO-INDUCED POLYCYCLIC AROMATIC HYDROCARBON TOXIC POTENTIALS OF NEAR SHORE LARVAL FISH HABITAT IN THE GREAT LAKES, USA

EPA Science Inventory

Photo-induced toxicity (PIT) of polycyclic aromatic hydrocarbons (PAH) has been documented in laboratory studies for both invertebrate and vertebrate aquatic organisms. PIT has not been verified in field studies for larval fish to date. Filtered water samples and larval fish were...

COMPARATIVE STUDIES OF THE EFFECT OF POLYCYCLIC AROMATIC HYDROCARBON GEOMETRY ON THE HYDROLYSIS OF DIOL EPOXIDES

EPA Science Inventory

Comparative studies of the effect of polycyclic aromatic hydrocarbon geometry on the hydrolysis of diol epoxides

The interaction of the diol epoxides (DEs) of both planar and non-planar PAHs with water have been examined using quantum mechanical and molecular dynamics. Th...

Determination of polycyclic aromatic hydrocarbons in biochar and biochar amended soil

USDA-ARS?s Scientific Manuscript database

A method for the determination of the 16 USEPA polycyclic aromatic hydrocarbons (PAHs) in biochar and soil amended with biochar was developed. Samples were Soxhlet extracted with acetone:cyclohexane 1:1, and PAHs were analysed by GC-MS after silica gel clean-up. In a comparative study based on reflu...

MEASUREMENT OF HIGH-MOLECULAR-WEIGHT POLYCYCLIC AROMATIC HYDROCARBONS IN SOILS BY PARTICLE BEAM HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) comprise a class of potentially hazardous compounds of concern to the U.S.EPA. The application of particle-beam (PB) liquid chromatography-mass spectrometry (LC-MS) to the measurement of high-molecular-weight PAHs was investigated. Instrume...

IMPACTS OF AGING ON IN VIVO AND IN VITRO MEASUREMENTS OF SOIL-BOUND POLYCYCLIC AROMATIC HYDROCARBON AVAILABILITY

EPA Science Inventory

Ingestion of contaminated soil is an exposure pathway at approximately one-half of the Superfund sites in the United States. This study was designed to evaluate the impacts of aging in soil on the availability of polycyclic aromatic hydrocarbons (PAHs). Two coal tar (CT)-amended ...

Preliminary Investigation into Pyrotechnic Chemical Products via Mass Spectrometry Techniques

DTIC Science & Technology

2015-03-11

i m u m ) Py/GC/MS: PVC 11 • Pyrolysis of PVC exclusively yield cyclic hydrocarbons – 24.3% benzyl derivatives and 75.6% polycyclic aromatic ...Determination of EPA’s priority pollutant polycyclic aromatic hydrocarbons in drinking waters by solid phase extraction-HPLC” Bruzzoniti et al., Anal... aromatic hydrocarbons (PAH) – 42.3% hydrocarbons , 53.5% phenols, 4.7% nitrogen-containing O NH OH OH N DISTRIBUTION STATEMENT A. Approved for public

Chemically bonded stationary phases that use synthetic hosts containing aromatic binding clefts: HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons.

PubMed Central

Zimmerman, S C; Saionz, K W; Zeng, Z

1993-01-01

The synthesis of hosts with improved binding affinities for nitroaromatic guests is described. Association constants for several host-guest complexes were measured in chloroform solution and ranged over three orders of magnitude. Two hosts were covalently linked to silica gel to produce chemically bonded stationary phases for HPLC. The use of these phases for HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons is discussed. PMID:8433981

Rapid estimation of concentration of aromatic classes in middistillate fuels by high-performance liquid chromatography

NASA Technical Reports Server (NTRS)

Otterson, D. A.; Seng, G. T.

1985-01-01

An high performance liquid chromatography (HPLC) method to estimate four aromatic classes in middistillate fuels is presented. Average refractive indices are used in a correlation to obtain the concentrations of each of the aromatic classes from HPLC data. The aromatic class concentrations can be obtained in about 15 min when the concentration of the aromatic group is known. Seven fuels with a wide range of compositions were used to test the method. Relative errors in the concentration of the two major aromatic classes were not over 10 percent. Absolute errors of the minor classes were all less than 0.3 percent. The data show that errors in group-type analyses using sulfuric acid derived standards are greater for fuels containing high concentrations of polycyclic aromatics. Corrections are based on the change in refractive index of the aromatic fraction which can occur when sulfuric acid and the fuel react. These corrections improved both the precision and the accuracy of the group-type results.

Exposure to daily ambient particulate polycyclic aromatic hydrocarbons and cough occurrence in adult chronic cough patients: A longitudinal study

NASA Astrophysics Data System (ADS)

Anyenda, Enoch Olando; Higashi, Tomomi; Kambayashi, Yasuhiro; Thao, Nguyen Thi Thu; Michigami, Yoshimasa; Fujimura, Masaki; Hara, Johsuke; Tsujiguchi, Hiromasa; Kitaoka, Masami; Asakura, Hiroki; Hori, Daisuke; Yamada, Yohei; Hayashi, Koichiro; Hayakawa, Kazuichi; Nakamura, Hiroyuki

2016-09-01

The specific components of airborne particulates responsible for adverse health effects have not been conclusively identified. We conducted a longitudinal study on 88 adult patients with chronic cough to evaluate whether exposure to daily ambient levels of particulate polycyclic aromatic hydrocarbons (PAH) has relationship with cough occurrence. Study participants were recruited at Kanazawa University Hospital, Japan and were physician-diagnosed to at least have asthma, cough variant asthma and/or atopic cough during 4th January to 30th June 2011. Daily cough symptoms were collected by use of cough diaries and simultaneously, particulate PAH content in daily total suspended particles collected on glass fiber filters were determined by high performance liquid chromatography coupled with fluorescence detector. Population averaged estimates of association between PAH exposure and cough occurrence for entire patients and subgroups according to doctor's diagnosis were performed using generalized estimating equations. Selected adjusted odds ratios for cough occurrence were 1.088 (95% confidence interval (CI): 1.031, 1.147); 1.209 (95% CI: 1.060, 1.379) per 1 ng/m3 increase for 2-day lag and 6-day moving average PAH exposure respectively. Likewise, 5 ring PAH had higher odds in comparison to 4 ring PAH. On the basis of doctor's diagnosis, non-asthma group had slightly higher odds ratio 1.127 (95% CI: 1.033, 1.228) per 1 ng/m3 increase in 2-day lag PAH exposure. Our findings suggest that ambient PAH exposure is associated with cough occurrence in adult chronic cough patients. The association may be stronger in non-asthma patients and even at low levels although there is need for further study with a larger sample size of respective diagnosis and inclusion of co-pollutants.

Bioaccessibility of polycyclic aromatic hydrocarbons in activated carbon or biochar amended vegetated (Salix viminalis) soil.

PubMed

Oleszczuk, Patryk; Godlewska, Paulina; Reible, Danny D; Kraska, Piotr

2017-08-01

The aim of the present study was to determine the effect of activated carbon (AC) or biochars on the bioaccessibility (C bioacc ) of polycyclic aromatic hydrocarbons (PAHs) in soils vegetated with willow (Salix viminalis). The study determined the effect of willow on the C bioacc PAHs and the effect of the investigated amendments on changes in dissolved organic carbon (DOC), crop yield and the content of PAHs in plants. PAH-contaminated soil was amended with 2.5 wt% AC or biochar. Samples from individual plots with and without plants were collected at the beginning of the experiment and after 3, 6, 12 and 18 months. The C bioacc PAHs were determined using sorptive bioaccessibility extraction (SBE) (silicon rods and hydroxypropyl-β-cyclodextrin). Both AC and biochar caused a decrease in the C bioacc PAHs. Immediately after adding AC, straw-derived biochar or willow-derived biochar to the soil, the reduction in the sum of 16 (Σ16) C bioacc PAHs was 70.3, 38.0, and 29.3%, respectively. The highest reduction of C bioacc was observed for 5- and 6-ring PAHs (from 54.4 to 100%), whereas 2-ring PAHs were reduced only 8.0-25.4%. The reduction of C bioacc PAHs increased over time. Plants reduced C bioacc in all soils although effects varied by soil treatment and PAH. Willow grown in AC- and biochar-amended soil accumulated less phenanthrene than in the control soil. The presence of AC in the soil also affected willow yield and shoot length and DOC was reduced from 53.5 to 66.9% relative to unamended soils. In the biochars-amended soil, no changes in soil DOC content were noted nor effects on willow shoot length. Copyright © 2017 Elsevier Ltd. All rights reserved.

Occurrence and distribution of Polycyclic aromatic hydrocarbons (PAHs) in seawater, sediments and corals from Hainan Island, China.

PubMed

Xiang, Nan; Jiang, Chunxia; Yang, Tinghan; Li, Ping; Wang, Haihua; Xie, Yanli; Li, Sennan; Zhou, Hailong; Diao, Xiaoping

2018-05-15

The levels of 16 US EPA priority polycyclic aromatic hydrocarbons (PAHs) were investigated in corals, ambient seawater and sediments of Hainan Island, China, using gas chromatography - mass spectrometry (GC-MS). The total PAHs (∑PAHs) concentrations ranged from 273.79 to 407.82ng/L in seawater. Besides, the concentrations of ∑PAHs in corals 333.88-727.03ng/g dw) were markedly (P < 0.05) higher than ambient sediments 67.29-196.99ng/g dw), demonstrating the bioaccumulation ability of PAHs by corals. The highest concentration of ∑PAHs was detected at site S2 in Pavona decussate, which also bore the highest ∑PAHs levels in both seawater and sediments. The massive corals were more enriched with PAHs than the branching corals. Although 2 and 3-ring PAHs were predominant and accounted for 69.27-80.46% of the ∑PAHs in corals and ambient environment, the levels of high molecular weight (HMW) PAHs (4-6 ring) in corals also demonstrated their potential dangers for corals and organisms around coral reefs. Biota-sediment accumulation factor (BSAF) refers to an index of the pollutant absorbed by aquatic organisms from the surrounding sediments. The poor correlation between log BSAF and log K ow (hydrophobicity) indicated that PAHs in corals maybe not bioaccumulate from the ambient sediments but through pathways like absorbing from seawater, symbiosis, and feeding. Based on our data, long-term ecological monitoring in typical coral reef ecosystems combined with ecotoxicological tests of PAHs on corals is necessary to determine the impacts of PAHs on coral reefs. Copyright © 2018 Elsevier Inc. All rights reserved.

Polycyclic aromatic hydrocarbons (PAHs) in atmospheric PM2.5 around 2013 Asian Youth Games period in Nanjing

NASA Astrophysics Data System (ADS)

Li, Xuxu; Kong, Shaofei; Yin, Yan; Li, Li; Yuan, Liang; Li, Qi; Xiao, Hui; Chen, Kui

2016-06-01

Eighteen polycyclic aromatic hydrocarbons (PAHs) in PM2.5 collected near the Nanjing Olympic Sports Center across the Asian Youth Games (AYG) period (from August 2 to August 28, 2013) were analyzed using GC-MS. Their levels, sources and health risks to human were discussed. Results showed that the total concentrations of PAHs in PM2.5 were 9.43, 7.21 and 8.83 ng m- 3 for pre- (August 3-15), during- (August 16-24) and post- (August 25-28) AYG periods, respectively. They were dominated by 5-ring and 6-ring PAHs. Total PAHs concentrations in PM2.5 during AYG period decreased by 24%, when compared with those for pre-AYG period. For combustion-derived PAHs and carcinogenic PAHs, they decreased by 26% and 21%, respectively. It implied that the pollution control measures implemented during the AYG can effectively reduce the emission of PAHs from various sources. The poor correlations between PAHs and meteorological parameters also favored that the variations of PAHs were raised by the changes of emission sources. Diagnostic ratios and principal component analysis revealed that vehicle emission and coal combustion were the predominant contributors, with minimal effects from biomass burning and petroleum. The health risks for human exposed to PAHs in PM2.5 were quantitatively assessed by BaP equivalent concentration (BaPeq) and the incremental lifetime cancer risk (ILCR). The estimated ILCR value of PAHs during the AYG periods decreased by 23% and 27% for children and adults when compared with those for the pre-AYG, respectively. It indicated that the pollution control measures reduced the risks of PAHs to sportsmen or human gathered around the Olympic Sport Center.

Soils impacted by PAHs: Would the stabilized organic matter be a green tool for the immobilization of these noxious compounds?

PubMed

Dores-Silva, Paulo R; Cotta, Jussara A O; Landgraf, Maria D; Rezende, Maria O O

2018-05-04

The objective of this study was to investigate the role of stabilized organic matter (vermicompost) and tropical soils in the sorption of naphthalene, anthracene and benzo[a]pyrene. The results obtained for the three compounds were extrapolated for the priority polycyclic aromatic hydrocarbons (PAHs) pollutants according to Environmental Protection Agency (US EPA). To evaluate the sorption process, high performance liquid chromatography was employed and the data was fitted by Freundlich isotherms. The results suggest that the sorption effect generally increases with the number of benzene rings of the PAHs, and that the persistence of PAHs in the environment is possibly related to the number of benzene rings in the PAH molecule. In addition, the pH of the vermicompost can strongly affect the adsorption process in this matrix.

Inorganic-organic hybrid coating material for the online in-tube solid-phase microextraction of monohydroxy polycyclic aromatic hydrocarbons in urine.

PubMed

Wang, ShuLing; Xu, Hui

2016-12-01

An inorganic-organic hybrid nanocomposite (zinc oxide/polypyrrole) that represents a novel kind of coating for in-tube solid-phase microextraction is reported. The composite coating was prepared by a facile electrochemical polymerization strategy on the inner surface of a stainless-steel tube. Based on the coated tube, a novel online in-tube solid-phase microextraction with liquid chromatography and mass spectrometry method was developed and applied for the extraction of three monohydroxy polycyclic aromatic hydrocarbons in human urine. The coating displayed good extraction ability toward monohydroxy polycyclic aromatic hydrocarbons. In addition, long lifespan, excellent stability, and good compression resistance were also obtained for the coating. The experimental conditions affecting the extraction were optimized systematically. Under the optimal conditions, the limits of detection and quantification were in the range of 0.039-0.050 and 0.130-0.167 ng/mL, respectively. Good linearity (0.2-100 ng/mL) was obtained with correlation coefficients larger than 0.9967. The repeatability, expressed as relative standard deviation, ranged between 2.5% and 9.4%. The method offered the advantage of process simplicity, rapidity, automation, and sensitivity in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities of Hubei province. An acceptable recovery of monohydroxy polycyclic aromatic hydrocarbons (64-122%) represented the additional attractive features of the method in real urine analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Removal of crude oil polycyclic aromatic hydrocarbons via organoclay-microbe-oil interactions.

PubMed

Ugochukwu, Uzochukwu C; Fialips, Claire I

2017-05-01

Clay minerals are quite vital in biogeochemical processes but the effect of organo-clays in the microbial degradation of crude oil polycyclic aromatic hydrocarbons is not well understood. The role of organo-saponite and organo-montmorillonite in comparison with the unmodified clays in crude oil polycyclic aromatic hydrocarbons (PAHs) removal via adsorption and biodegradation was studied by carrying out microcosm experiments in aqueous clay/oil systems with a hydrocarbon degrading microbial community that is predominantly alcanivorax spp. Montmorillonite and saponite samples were treated with didecyldimethylammonium bromide to produce organo-montmorillonite and organo-saponite used in this study. Obtained results indicate that clays with high cation exchange capacity (CEC) such as montmorillonite produced organo-clay (organomontmorillonite) that was not stimulatory to biodegradation of crude oil polycyclic aromatic compounds, especially the low molecular weight (LMW) ones, such as dimethylnaphthalenes. It is suggested that interaction between the organic phase of the organo-clay and the crude oil PAHs which is hydrophobic in nature must have reduced the availability of the polycyclic aromatic hydrocarbons for biodegradation. Organo-saponite did not enhance the microbial degradation of dimethylnaphthalenes but enhanced the biodegradation of some other PAHs such as phenanthrene. The unmodified montmorillonite enhanced the microbial degradation of the PAHs and is most likely to have done so as a result of its high surface area that allows the accumulation of microbes and nutrients enhancing their contact. Copyright © 2017 Elsevier Ltd. All rights reserved.

Emission factors of polycyclic and nitro-polycyclic aromatic hydrocarbons from residential combustion of coal and crop residue pellets.

PubMed

Yang, Xiaoyang; Liu, Shijie; Xu, Yisheng; Liu, Yu; Chen, Lijiang; Tang, Ning; Hayakawa, Kazuichi

2017-12-01

Polycyclic aromatic hydrocarbons (PAHs) and nitro-polycyclic aromatic hydrocarbons (NPAHs) are toxic pollutants mainly produced during fossil fuel combustion. Domestic coal stoves, which emit large amounts of PAHs and NPAHs, are widely used in the Chinese countryside. In this study, emission factors (Efs) for 13 PAH species and 21 NPAH species for four raw coal (three bituminous and one anthracite), one honeycomb briquette, and one crop residue pellet (peanut hulls) samples burned in a typical Chinese rural cooking stove were determined experimentally. The PAH and NPAH Efs for the six fuels were 3.15-49 mg/kg and 0.32-100 μg/kg, respectively. Peanut hulls had very high Efs for both PAHs and NPAHs, and honeycomb briquettes had the lowest Efs. 2-Nitropyrene and 2-nitrofluoranthene, which are NPAHs typically found in secondary organic aerosol, were detected in the emissions from some fuels, suggesting that chemical reactions may have occurred in the dilution tunnel between the flue gas leaving the stove and entering the sampler. The 1-nitropyrene to pyrene diagnostic ratios for coal and peanut hulls were 0.0001 ± 0.0001 and 0.0005, respectively. These were in the same order of magnitude as reference ratios for emissions during coal combustion. The 6-nitrobenzo[a]pyrene to benzo[a]pyrene ratios for the fuels were determined, and the ratios for coal and peanut hulls were 0.0010 ± 0.0001 and 0.0014, respectively. The calculated potential toxic risks indicated that peanut hull emissions were very toxic, especially in terms of NPAHs, compared with emissions from the other fuels. Copyright © 2017 Elsevier Ltd. All rights reserved.

Differentiating the roles of photooxidation and biodegradation in the weathering of Light Louisiana Sweet crude oil in surface water from the Deepwater Horizon site.

PubMed

Bacosa, Hernando P; Erdner, Deana L; Liu, Zhanfei

2015-06-15

We determined the contributions of photooxidation and biodegradation to the weathering of Light Louisiana Sweet crude oil by incubating surface water from the Deepwater Horizon site under natural sunlight and temperature conditions. N-alkane biodegradation rate constants were ca. ten-fold higher than the photooxidation rate constants. For the 2-3 ring and 4-5 ring polycyclic aromatic hydrocarbons (PAHs), photooxidation rate constants were 0.08-0.98day(-1) and 0.01-0.07day(-1), respectively. The dispersant Corexit enhanced degradation of n-alkanes but not of PAHs. Compared to biodegradation, photooxidation increased transformation of 4-5 ring PAHs by 70% and 3-4 ring alkylated PAHs by 36%. For the first time we observed that sunlight inhibited biodegradation of pristane and phytane, possibly due to inhibition of the bacteria that can degrade branched-alkanes. This study provides quantitative measures of oil degradation under relevant field conditions crucial for understanding and modeling the fate of spilled oil in the northern Gulf of Mexico. Copyright © 2015 Elsevier Ltd. 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 hydrocarbon migration from creosote-treated railway ties into ballast and adjacent wetlands

Treesearch

Kenneth M. Brooks

2004-01-01

Occasionally, creosote-treated railroad ties need to be replaced, sometimes in sensitive environments such as wetlands. To help determine if this is detrimental to the surrounding environment, more information is needed on the extent and pattern of creosote, or more specifically polycyclic aromatic hydrocarbon (PAH), migration from railroad ties and what effects this...

CTEPP STANDARD OPERATING PROCEDURE FOR EXTRACTING AND PREPARING URINE SAMPLES FOR ANALYSIS OF HYDROXY POLYCYCLIC AROMATIC HYDROCARBONS, PENTACHLOROPHENOL AND 2,4-D (SOP-5.21)

EPA Science Inventory

The method for extracting and preparing urine samples for analysis of hydroxy-polycyclic aromatic hydrocarbons, pentachlorophenol and 2,4-D is summarized in this SOP. It covers the extraction, concentration and methylation of samples that are to be analyzed by gas chromatography/...

Watershed-based sources of polycyclic aromatic hydrocarbons in urban storm water.

PubMed

Stein, Eric D; Tiefenthaler, Liesl L; Schiff, Kenneth

2006-02-01

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic and mutagenic compounds, ubiquitous in the air and water of urban environments, and have been shown to accumulate in coastal estuarine and marine sediments. Although previous studies have documented concentrations and loads of PAHs in urban runoff, little is known about the sources and temporal patterns of PAH loading from storm water. This study characterized the sources and temporal patterns of PAHs in urban storm water by analyzing PAH concentrations and loads from a range of homogeneous land use sites and in-river mass emission sites throughout the greater Los Angeles, California, USA, region. Samples were collected at 30- to 60-min intervals over the course of a storm during multiple storm events over a four-year period in order to investigate PAH sources and inter- and intrastorm patterns in loading. Polycyclic aromatic hydrocarbon storm fluxes ranged from 1.3 g/km2 for the largely undeveloped Arroyo Sequit watershed to 223.7 g/km2 for the highly urbanized Verdugo Wash watershed, with average storm fluxes being 46 times higher in developed versus undeveloped watersheds. Early-season storms repeatedly produced substantially higher loads than comparably sized late-season storms. Within individual storms, PAHs exhibited a moderate first flush with between 30 and 60% of the total PAH load being discharged in the first 20% of the storm volume. The relative distribution of individual PAHs demonstrated a consistent predominance of high-molecular-weight compounds indicative of pyrogenic sources.

Quasi-targeted analysis of hydroxylation-related metabolites of polycyclic aromatic hydrocarbons in human urine by liquid chromatography-mass spectrometry.

PubMed

Tang, Caiming; Tan, Jianhua; Fan, Ruifang; Zhao, Bo; Tang, Caixing; Ou, Weihui; Jin, Jiabin; Peng, Xianzhi

2016-08-26

Metabolite identification is crucial for revealing metabolic pathways and comprehensive potential toxicities of polycyclic aromatic hydrocarbons (PAHs) in human body. In this work, a quasi-targeted analysis strategy was proposed for metabolite identification of monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in human urine using liquid chromatography triple quadruple mass spectrometry (LC-QqQ-MS/MS) combined with liquid chromatography high resolution mass spectrometry (LC-HRMS). Potential metabolites of OH-PAHs were preliminarily screened out by LC-QqQ-MS/MS in association with filtering in a self-constructed information list of possible metabolites, followed by further identification and confirmation with LC-HRMS. The developed method can provide more reliable and systematic results compared with traditional untargeted analysis using LC-HRMS. In addition, data processing for LC-HRMS analysis were greatly simplified. This quasi-targeted analysis method was successfully applied to identifying phase I and phase II metabolites of OH-PAHs in human urine. Five metabolites of hydroxynaphthalene, seven of hydroxyfluorene, four of hydroxyphenanthrene, and three of hydroxypyrene were tentatively identified. Metabolic pathways of PAHs in human body were putatively revealed based on the identified metabolites. The experimental results will be valuable for investigating the metabolic processes of PAHs in human body, and the quasi-targeted analysis strategy can be expanded to the metabolite identification and profiling of other compounds in vivo. Copyright © 2016 Elsevier B.V. All rights reserved.

Redox shuttles having an aromatic ring fused to a 1,1,4,4-tetrasubstituted cyclohexane ring

DOEpatents

Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

2015-12-01

An electrolyte includes an alkali metal salt; an aprotic solvent; and a redox shuttle additive including an aromatic compound having at least one aromatic ring fused with at least one non-aromatic ring, the aromatic ring having two or more oxygen or phosphorus-containing substituents.

Tholins: Can They Provide a Substrate, Carbon and Nitrogen for Plant Production?

NASA Technical Reports Server (NTRS)

Wignarajah, Kanapathipillai; Khare, Bishun; Cruikshank, Dale; McKay, Christopher; Arnold, James O. (Technical Monitor)

1999-01-01

Tholin is a word coined to describe the entire class of complex organic solids produced in laboratory experiments where pre-biotic gaseous chemicals are subject to bombardment by high energy. The atomic composition of Titan tholin produced from 10 percent CH4 and 90 percent N2 in a simulation of Titan atmosphere irradiated by charged particles trapped in the magnetosphere of Saturn gave 67 percent C and 33 percent N. Hydrolysis of Titan tholin with 6N HCl produced a racemic mixture of biological and non-biological amino acids that was confirmed by GC/MS. Other tholins, that revealed the presence of amino acids, were UV tholin produced under possible primitive Earth conditions by irradiation of a mixture of gases (CH4, C2H6, NH3, H2S and liquid H2O) with long-wavelength ultraviolet light, representing the most abundant useful energy source for prebiological organic synthesis; Spark tholin in a crude simulation of Jupiter atmosphere using electrical discharge through a mixture of CH4, NH3, and H2O vapor. Pyrolytic GC/MS of Titan tholin produced more than one hundred organic compounds including saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. Similar rich pyrolytic products were obtained with UV as well as Spark tholins. A range of two to four ring PAHs (Polycyclic Aromatic Hydrocarbons) in Spark as well as Titan tholins, some with one to four alkylation sites, were identified by two-step laser desorption/multiphoton ionization mass spectrometry and also confirmed by the synchronous fluorescence technique. Previous studies have demonstrated the potential for use of tholins as a source of carbon and energy by microbes. This paper describes studies that evaluate the potential for using different types of tholins as (a) a substrate for growing plants and (b) a source of carbon and nitrogen for plants. The data are interpreted in terms of the potential for using such tholins to grow plants for food in extraterrestrial habitats and also to speculate on the possibilities of abiotic evolution of plants.

Highly dispersed buckybowls as model carbocatalysts for C–H bond activation

DOE PAGES

Soykal, I. Ilgaz; Wang, Hui; Park, Jewook; ...

2015-03-19

Buckybowl fractions dispersed on mesoporous silica constitute an ideal model for studying the catalysis of graphitic forms of carbon since the dispersed carbon nanostructures contain a high ratio of edge defects and curvature induced by non-six-membered rings. Dispersion of the active centers on an easily accessible high surface area material allowed for high density of surface active sites associated with oxygenated structures. This report illustrates a facile method of creating model polycyclic aromatic nano-structures that are not only active for alkane C-H bond activation and oxidative dehydrogenation but also can be practical catalysts to be eventually used in industry.

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

PubMed

Zafra, German; Cortés-Espinosa, Diana V

2015-12-01

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

Optimization of multiwalled carbon nanotubes reinforced hollow-fiber solid-liquid-phase microextraction for the determination of polycyclic aromatic hydrocarbons in environmental water samples using experimental design.

PubMed

Hamedi, Raheleh; Hadjmohammadi, Mohammad Reza

2017-09-01

A novel design of hollow-fiber liquid-phase microextraction containing multiwalled carbon nanotubes as a solid sorbent, which is immobilized in the pore and lumen of hollow fiber by the sol-gel technique, was developed for the pre-concentration and determination of polycyclic aromatic hydrocarbons in environmental water samples. The proposed method utilized both solid- and liquid-phase microextraction media. Parameters that affect the extraction of polycyclic aromatic hydrocarbons were optimized in two successive steps as follows. Firstly, a methodology based on a quarter factorial design was used to choose the significant variables. Then, these significant factors were optimized utilizing central composite design. Under the optimized condition (extraction time = 25 min, amount of multiwalled carbon nanotubes = 78 mg, sample volume = 8 mL, and desorption time = 5 min), the calibration curves showed high linearity (R 2  = 0.99) in the range of 0.01-500 ng/mL and the limits of detection were in the range of 0.007-1.47 ng/mL. The obtained extraction recoveries for 10 ng/mL of polycyclic aromatic hydrocarbons standard solution were in the range of 85-92%. Replicating the experiment under these conditions five times gave relative standard deviations lower than 6%. Finally, the method was successfully applied for pre-concentration and determination of polycyclic aromatic hydrocarbons in environmental water samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas-phase reactions of phenyl radicals with aromatic molecules

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

Fahr, A.; Stein, S.E.

1988-08-25

Relative rates of reactions of phenyl radicals with a series of aromatic and polycyclic aromatic compounds are reported. Most studies were done in static reactors at 450/degrees/C using diphenyl diketone (benzil) as the phenyl radical source. Reactions with the following molecules are reported: benzene, toluene, p-xylene, 1,3,5-trimethylbenzene, phenol, bromobenzene, naphthalene, biphenyl, anthracene, 9-methylanthracene, and triphenylene. For reactions with substituted benzenes, H abstraction is the dominant reaction. Relative rates of phenylation at different sites do not closely follow established trends for rates of radical attack. It is proposed that these deviations are primarily due to a dependence of the degree ofmore » reversibility on the specific site of phenylation. These studies also show that the rates of phenyl and H-atom migration around the ring in adduct radicals are slow relative to dissociation. Also, by use of these results to link literature rate data from high and low temperatures, a rate expression for H abstraction from p-xylene by phenyl of 10/sup 9.6/ exp(-4.4 kcal/RT) M/sup /minus/1/ s/sup /minus/1/ is derived.« less

Characterization of polycyclic aromatic hydrocarbons and metals in ashes released from a forest fire

NASA Astrophysics Data System (ADS)

Campos, I.; Abrantes, N.; Pereira, P.; Vale, C.; Ferreira, A.; Keizer, J. J.

2012-04-01

Wildfires have become a permanent source of environmental and societal concerns. Whilst the impacts of wildfire on hydrological and erosion processes are well documented, the stocks and export of polycyclic aromatic hydrocarbons (PAHs) and heavy metals have received considerably less research attention. The ashes produced by wildfires, which include polluting substances such as PAHs and metals, are subject to transport processes by wind and especially by overland flow and water infiltrating into the soil and possibly reaching ground water bodies. In the framework of the FIRECNUTS project, we are studying the stocks of PAHs and selected metals in recently burnt forest stands in north-central Portugal, and their subsequent export by overland flow. The present work, however, will focus on the stocks in the ashes, both immediately after wildfire and three months later. These ashes were collected at two burnt slopes with contrasting forest types, i.e. a eucalypt and a maritime pine stand, the two pre-dominant forest types in the study region. The sixteen PAHs identified by US EPA as priority contaminants were analysed by gas chromatograph, after extraction and column clean up. The contents of vanadium (V), chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd) and lead (Pb) were analysed by inductively coupled plasma- mass spectrometry (ICP-MS), after an acid digestion, while mercury (Hg) was analysed by pyrolysis atomic absorption spectrometry with gold amalgamation. The total concentration of PAHs immediately after the wildfire ranged from 314 ng/g dry weight in the maritime pine stand to 597 ng/g dry weight in the eucalypt stand. Three months later, the total concentration has decreased with 33% in the pine stand but only half (16%) in the eucalypt stand. The composition the PAHs by ring size was dominated by three-rings PAHs. This was true for all samples. The concentrations of various metals differed for the two sampling occasions but not in straightforward manners. Some metals (Co, Ni, Cu, Zn, Cd, Pb and Hg) revealed higher contents immediately after the fire, whereas others (V, Cr and As) did three months later. The present results underline the importance of furthering the knowledge about contamination of soil and water by ashes from wildfires and the associated risks in terms of ecotoxicological effects, both in-situ and in downstream aquatic systems. Keywords: Polycyclic aromatic hydrocarbons (PAH); heavy metals; stocks; ash; wildfires

Regional-scale simulation of transport and transformations of semi-volatile polycyclic aromatic hydrocarbons (PAHs) in East Asia: diurnal variations investigation

NASA Astrophysics Data System (ADS)

Mu, Qing; Lammel, Gerhard; Cheng, Yafang

2015-04-01

Semi-volatile PAHs are major pollutants of urban air, mostly regionally transported and reaching remote environments[1]. Some semi-volatile PAHs are carcinogenic. About 22% of global PAHs emissions are in China. The transport and sinks (atmospheric reactions, deposition) of semi-volatile PAHs in East Asia are studied using a modified version of the Weather Research and Forecasting model coupled with chemistry (WRF/Chem [2]). For this purpose, PAHs' gas and particulate phase chemical reactions and dry and wet deposition processes are included. We use emissions of 2008 [3] which include technical combustion processes (coal, oil, gas, waste and biomass) and open fires and apply diurnal time functions as those of black carbon. The model was run for phenanthrene (3-ring PAH, p = 1.5×10-2 Pa at 298 K) and benzo(a)pyrene (5-ring PAH, p = 7×10-7 Pa) for July 2013 with hourly output and 27 km horizontal grid spacing. The comparison of model predicted phenanthrene concentrations with measurements at a rural site near Beijing (own data, unpublished) validates the model's ability to simulate diurnal variations of gaseous PAHs. The model's performance is better in simulating day time than night time gaseous PAHs. The concentrations of PAHs had experienced significant diurnal variations in rural and remote areas of China. Elevated concentration levels of 40-60 ng m-3 for phenanthrene and 1-10 ng m-3 for benzo(a)pyrene are predicted in Shanxi, Guizhou, the North China Plain, the Sichuan Basin and Chongqing metropolitan areas due to the high emission densities at those locations. References [1] Keyte, I.J., Harrison, R.M., and Lammel, G., 2013: Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons - a review, Chem. Soc. Rev., 42, 9333-9391. [2] Grell, G.A, Peckham, S.E, Schmitz, R, McKeen, S.A, Frost, G, Skamarock, W.C, and Eder, B., 2005: Fully coupled online chemistry within the WRF model, Atmos. Environ., 39, 6957-6975. [3] Shen, H. Z., Huang, Y., Wang, R., Zhu, D., Li, W., Shen, G. F., Wang, B., Zhang, Y. Y., Chen, Y. C., Lu, Y., Chen, H., Li, T. C., Sun, K., Li, B. G., Liu, W. X., Liu, J. F., and Tao, S., 2013: Global atmospheric emissions of polycyclic aromatic hydrocarbons from 1960 to 2008 and future predictions, Environ. Sci. Technol., 47, 6415-6424.

"Super-Reducing" Photocatalysis: Consecutive Energy and Electron Transfers with Polycyclic Aromatic Hydrocarbons.

PubMed

Brasholz, Malte

2017-08-21

Donation welcome: Recent developments in visible-light photocatalysis allow the utilization of increasingly negative reduction potentials. Successive energy and electron transfer with polycyclic aromatic hydrocarbons enables the catalytic formation of strongly reducing arene radical anions, classical stoichiometric reagents for one-electron reduction in organic synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Moss as bio-indicators of human exposure to polycyclic aromatic hydrocarbons in Portland, OR

Treesearch

Geoffrey H. Donovan; Sarah E. Jovan; Demetrios Gatziolis; Vicente J. Monleon

2015-01-01

Polycyclic aromatic hydrocarbons (PAHs) are a class of air pollutants linked to a wide range of adverse health outcomes, including asthma, cancers, cardiovascular disease, and fetal growth impairment. PAHs are emitted by combustion of organic matter (e.g. fossil fuels, plant biomass) and can accumulate in plant and animal tissues over time. Compared to criteria...

LASER DESORPTION-IONIZATION OF POLYCYCLIC AROMATIC HYDROCARBONS FROM GLASS SURFACES WITH ION MOBILITY SPECTROMETRY ANALYSIS. (R826769)

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) were analyzed as adsorbates on borosilicate glass at levels from 40 pg (5.5 pg mm^-2) to 7 g (1 

Coal-tar-based pavement sealcoat, polycyclic aromatic Hydrocarbons (PAHs), and environmental health

USGS Publications Warehouse

Mahler, B.J.; Van Metre, P.C.

2011-01-01

Studies by the U.S. Geological Survey (USGS) have identified coal-tar-based sealcoat-the black, viscous liquid sprayed or painted on asphalt pavement such as parking lots-as a major source of polycyclic aromatic hydrocarbon (PAH) contamination in urban areas for large parts of the Nation. Several PAHs are suspected human carcinogens and are toxic to aquatic life.

Concentration profiles, source apportionment and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in dumpsite soils from Agbogbloshie e-waste dismantling site, Accra, Ghana.

PubMed

Daso, Adegbenro P; Akortia, Eric; Okonkwo, Jonathan O

2016-06-01

The concentrations of eighteen (18) polycyclic aromatic hydrocarbons (PAHs), including the 16 USEPA's priority PAHs as well as two alkyl-substituted naphthalenes were determined in dumpsite soils collected from different sampling sites within the Agbogbloshie e-waste dismantling site in Accra, Ghana. Following their isolation with ultrasonic-assisted extraction technique, the concentrations of the PAHs were determined by gas chromatography mass spectrometry (GC-MS). Loss-on-ignition (LOI) method was employed for the determination of total organic carbon (TOC) of the soil samples. The mean Σ18PAHs obtained were 3006, 5627, 3046, 5555, and 7199 ng g(-1) dry weight (dw) for sampling sites A (mosque), B (dismantling site), C (residential house/police station), D (personal computer repairers' shop) and E (e-waste open burning area), respectively. In all cases, the prevalence of phenanthrene, fluoranthene and pyrene was generally observed across the sampling sites. In this study, PAHs with two to three rings and four to six rings exhibited strong positive correlations, whereas BbF and BkF showed weak positive and negative correlations with other PAHs investigated. With the exception of BbF and BkF, all the PAHs had moderate to strong positive correlations with the TOC. Benzo[a]pyrene equivalent (BaPeq) concentration is a useful indicator of the carcinogenic potency of environmental matrices and these ranged between 111 and 454 ng g(-1), which are generally below the 'safe' level of 600 ng g(-1) established for the protection of the environment and human health. Interestingly, the seven carcinogenic PAHs were the major contributors to the BaPeq concentrations accounting between 97.7 and 98.3 %. Despite the minimal risk to cancer via exposure to the investigated dumpsite soil as indicated in the present study, the prolonged exposure to these pollutants via various exposure pathways may result in increased risk to cancer over time. The application of several methodological approaches for PAH source apportionment, including the use of molecular diagnostic ratios, mostly implicated pyrogenic processes as the main sources of PAHs into the investigated dumpsite soils. Furthermore, their compositional profiles across the sampling sites also suggest similar sources of PAHs into the dumpsite soil.

Determination of descriptors for polycyclic aromatic hydrocarbons and related compounds by chromatographic methods and liquid-liquid partition in totally organic biphasic systems.

PubMed

Ariyasena, Thiloka C; Poole, Colin F

2014-09-26

Retention factors on several columns and at various temperatures using gas chromatography and from reversed-phase liquid chromatography on a SunFire C18 column with various mobile phase compositions containing acetonitrile, methanol and tetrahydrofuran as strength adjusting solvents are combined with liquid-liquid partition coefficients in totally organic biphasic systems to calculate descriptors for 23 polycyclic aromatic hydrocarbons and eighteen related compounds of environmental interest. The use of a consistent protocol for the above measurements provides descriptors that are more self consistent for the estimation of physicochemical properties (octanol-water, air-octanol, air-water, aqueous solubility, and subcooled liquid vapor pressure). The descriptor in this report tend to have smaller values for the L and E descriptors and random differences in the B and S descriptors compared with literature sources. A simple atom fragment constant model is proposed for the estimation of descriptors from structure for polycyclic aromatic hydrocarbons. The new descriptors show no bias in the prediction of the air-water partition coefficient for polycyclic aromatic hydrocarbons unlike the literature values. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposites as an adsorbent for the fast determination of 16 priority polycyclic aromatic hydrocarbons in aqueous samples.

PubMed

Chen, Kun; Jin, Rongrong; Luo, Chen; Song, Guoxin; Hu, Yaoming; Cheng, Hefa

2018-04-01

A novel adsorbent made of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposite was synthesized and applied to determine 16 priority polycyclic aromatic hydrocarbons by magnetic solid phase extraction in water samples. FTIR spectroscopy, transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy consistently indicate that the synthesized adsorbents are made of core-shell nanoparticles well dispersed on the surface of graphene and carbon nanotubes. The major factors affecting the extraction efficiency, including the pH value of samples, the amount of adsorbent, adsorption time and desorption time, type and volume of desorption solvent, were systematically optimized. Under the optimum extraction conditions, a linear response was obtained for polycyclic aromatic hydrocarbons between concentrations of 10 and 500 ng/L with the correlation coefficients ranging from 0.9958 to 0.9989, and the limits of detection (S/N = 3) were between 0.1 and 3.0 ng/L. Satisfactory results were also obtained when applying these magnetic graphene/carbon nanotubes/polydopamine hybrid nanocomposites to detect polycyclic aromatic hydrocarbons in several environmental aqueous samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

NASA Technical Reports Server (NTRS)

Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.; Gillette, J. S.; Clemett, S. J.; Zare, R. N.

1999-01-01

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

Four-dimensional data coupled to alternating weighted residue constraint quadrilinear decomposition model applied to environmental analysis: Determination of polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Liu, Tingting; Zhang, Ling; Wang, Shutao; Cui, Yaoyao; Wang, Yutian; Liu, Lingfei; Yang, Zhe

2018-03-01

Qualitative and quantitative analysis of polycyclic aromatic hydrocarbons (PAHs) was carried out by three-dimensional fluorescence spectroscopy combining with Alternating Weighted Residue Constraint Quadrilinear Decomposition (AWRCQLD). The experimental subjects were acenaphthene (ANA) and naphthalene (NAP). Firstly, in order to solve the redundant information of the three-dimensional fluorescence spectral data, the wavelet transform was used to compress data in preprocessing. Then, the four-dimensional data was constructed by using the excitation-emission fluorescence spectra of different concentration PAHs. The sample data was obtained from three solvents that are methanol, ethanol and Ultra-pure water. The four-dimensional spectral data was analyzed by AWRCQLD, then the recovery rate of PAHs was obtained from the three solvents and compared respectively. On one hand, the results showed that PAHs can be measured more accurately by the high-order data, and the recovery rate was higher. On the other hand, the results presented that AWRCQLD can better reflect the superiority of four-dimensional algorithm than the second-order calibration and other third-order calibration algorithms. The recovery rate of ANA was 96.5% 103.3% and the root mean square error of prediction was 0.04 μgL- 1. The recovery rate of NAP was 96.7% 115.7% and the root mean square error of prediction was 0.06 μgL- 1.

Hydrocarbons on Phoebe, Iapetus, and Hyperion: Quantitative Analysis

NASA Technical Reports Server (NTRS)

Cruikshank, Dale P.; MoreauDalleOre, Cristina; Pendleton, Yvonne J.; Clark, Roger Nelson

2012-01-01

We present a quantitative analysis of the hydrocarbon spectral bands measured on three of Saturn's satellites, Phoebe, Iaperus, and Hyperion. These bands, measured with the Cassini Visible-Infrared Mapping Spectrometer on close fly-by's of these satellites, are the C-H stretching modes of aromatic hydrocarbons at approximately 3.28 micrometers (approximately 3050 per centimeter), and the are four blended bands of aliphatic -CH2- and -CH3 in the range approximately 3.36-3.52 micrometers (approximately 2980- 2840 per centimeter) bably indicating the presence of polycyclic aromatic hydrocarbons (PAH), is unusually strong in comparison to the aliphatic bands, resulting in a unique signarure among Solar System bodies measured so far, and as such offers a means of comparison among the three satellites. The ratio of the C-H bands in aromatic molecules to those in aliphatic molecules in the surface materials of Phoebe, NAro:NAliph approximately 24; for Hyperion the value is approximately 12, while laperus shows an intermediate value. In view of the trend of the evolution (dehydrogenation by heat and radiation) of aliphatic complexes toward more compact molecules and eventually to aromatics, the relative abundances of aliphatic -CH2- and -CH3- is an indication of the lengths of the molecular chain structures, hence the degree of modification of the original material. We derive CH2:CH3 approximately 2.2 in the spectrum of low-albedo material on laperus; this value is the same within measurement errors to the ratio in the diffuse interstellar medium. The similarity in the spectral signatures of the three satellites, plus the apparent weak trend of aromatic/aliphatic abundance from Phoebe to Hyperion, is consistent with, and effectively confirms that the source of the hydrocarbon-bearing material is Phoebe, and that the appearance of that material on the other two satellites arises from the deposition of the inward-spiraling dust that populates the Phoebe ring.

LOW TEMPERATURE FORMATION OF NITROGEN-SUBSTITUTED POLYCYCLIC AROMATIC HYDROCARBONS (PANHs)—BARRIERLESS ROUTES TO DIHYDRO(iso)QUINOLINES

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

Parker, Dorian S. N.; Yang, Tao; Dangi, Beni B.

Meteorites contain bio-relevant molecules such as vitamins and nucleobases, which consist of aromatic structures with embedded nitrogen atoms. Questions remain over the chemical mechanisms responsible for the formation of nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) in extraterrestrial environments. By exploiting single collision conditions, we show that a radical mediated bimolecular collision between pyridyl radicals and 1,3-butadiene in the gas phase forms nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) 1,4-dihydroquinoline and to a minor amount 1,4-dihydroisoquinoline. The reaction proceeds through the formation of a van der Waals complex, which circumnavigates the entrance barrier implying it can operate at very low kinetic energy and thereforemore » at low temperatures of 10 K as present in cold molecular clouds such as TMC-1. The discovery of facile de facto barrierless exoergic reaction mechanisms leading to PANH formation could play an important role in providing a population of aromatic structures upon which further photo-processing of ice condensates could occur to form nucleobases.« less

Polycyclic Aromatic Hydrocarbons and Astrophysics: The State of the Pah Model and a Possible Tracer of Nitrogen in Carbon-Rich Dust

NASA Technical Reports Server (NTRS)

Hudgins, Douglas M.; Allamandola, Louis J.

2003-01-01

Over the past fifteen years, thanks to significant, parallel advancements in observational, experimental, and theoretical techniques, tremendous strides have been made in our understanding of the role aromatic materials play in the interstellar medium (ISM). Twenty years ago, the possible existence of an abundant population of large, carbon-rich molecules in the ISM was unthinkable. Today, the unmistakable spectroscopic signatures of polycyclic aromatic hydrocarbon molecules (PAHs) - shockingly large molecules by the standards of traditional interstellar chemistry - are recognized throughout the Universe. In this paper, we will examine the current state of the interstellar PAH model and its utility as a diagnostic tool to derive insight into the nature of the interstellar PAH population. As an example of this application, we will examine the results of our recent spectroscopic studies of polycyclic aromatic nitrogen heterocycles (PANHs)-PAHs with an atom of nitrogen substituted into the aromatic skeleton-and discuss a possible tracer of such species amongst the interstellar PAH emission bands in the latest observational data.

Analysis of Parent/Nitrated Polycyclic Aromatic Hydrocarbons in Particulate Matter 2.5 Based on Femtosecond Ionization Mass Spectrometry.

PubMed

Itouyama, Noboru; Matsui, Taiki; Yamamoto, Shigekazu; Imasaka, Tomoko; Imasaka, Totaro

2016-02-01

Particulate matter 2.5 (PM2.5), collected from ambient air in Fukuoka City, was analyzed by gas chromatography combined with multiphoton ionization mass spectrometry using an ultraviolet femtosecond laser (267 nm) as the ionization source. Numerous parent polycyclic aromatic hydrocarbons (PPAHs) were observed in a sample extracted from PM2.5, and their concentrations were determined to be in the range from 30 to 190 pg/m(3) for heavy PPAHs. Standard samples of nitrated polycyclic aromatic hydrocarbons (NPAHs) were examined, and the limits of detection were determined to be in the picogram range. The concentration of NPAH adsorbed on PM2.5 in the air was less than 900-1300 pg/m(3). Graphical Abstract ᅟ.

Degradation of polycyclic aromatic hydrocarbons (PAHs) by a mixed culture and its component pure cultures, obtained from PAH-contaminated soil.

PubMed

Trzesicka-Mlynarz, D; Ward, O P

1995-06-01

A mixed culture, isolated from soil contaminated with polycyclic aromatic hydrocarbons (PAHs), grew on and degraded fluoranthene in aqueous media supplemented with glucose, yeast extract, and peptone. Increased complex nitrogen levels in the medium promoted bacterial growth and a greater extent of fluoranthene degradation. Amendment of the media with high glucose levels also diminished specific fluoranthene degradation. The mixed culture was capable of degrading a range of other PAHs, including benzo[a]pyrene, anthracene, phenanthrene, acenaphthene, and fluorene. The mixed culture contained four predominant isolates, all of which were Gram-negative rods, three of which were identified as Pseudomonas putida, Flavobacterium sp., and Pseudomonas aeruginosa. Better degradation of a defined PAH mixture was observed with the mixed culture than with individual isolates. A reconstituted culture, prepared by combining the four individual isolates, manifested a similar PAH biodegradation performance to the original mixed culture. When compared with the mixed culture, individual isolates exhibited a relatively good capacity to remove more water-soluble PAHs (acenaphthene, fluorene, phenanthrene, fluoranthene). In contrast, removal of less water-soluble PAHs (anthracene and pyrene) was low or negligible with isolated cultures compared with the mixed culture.

Total Synthesis of Natural Products Using Hypervalent Iodine Reagents

NASA Astrophysics Data System (ADS)

Maertens, Gaetan; L'homme, Chloe; Canesi, Sylvain

2014-12-01

We present a review of natural product syntheses accomplished in our laboratory during the last five years. Each synthetic route features a phenol dearomatization promoted by an environmentally benign hypervalent iodine reagent. The dearomatizations demonstrate the “aromatic ring umpolung” concept, and involve stereoselective remodeling of the inert unsaturations of a phenol into a highly functionalized key intermediate that may contain a quaternary carbon center and a prochiral dienone system. Several new oxidative strategies were employed, including transpositions (1,3-alkyl shift and Prins-pinacol), a polycyclization, an ipso rearrangement, and direct nucleophilic additions at the phenol para position. Several alkaloids, heterocyclic compounds, and a polycyclic core have been achieved, including sceletenone (a serotonin reuptake inhibitor), acetylaspidoalbidine (an antitumor agent), fortucine (antiviral and antitumor), erysotramidine (curare-like effect), platensimycin (an antibiotic), and the main core of a kaurane diterpene (immunosuppressive agent and stimulator of apoptosis). These concise and in some cases enantioselective syntheses effectively demonstrate the importance of hypervalent iodine reagents in the total synthesis of bioactive natural products.

Ten-year Pollution Characteristics of Particulate-associated Polycyclic Aromatic Hydrocarbons in Beijing, China

NASA Astrophysics Data System (ADS)

Zhu, Xianlei; Deng, Changjiang; Biandan, Luobu; Fu, Xianqiang; Mu, Xilong

2015-04-01

Polycyclic aromatic hydrocarbons (PAHs) are well-known air pollutants of health concern. However, they are not listed as routinely measured pollutants in China, in spite of benzo[a]pyrene (BaP) being included in the National Ambient Air Quality Standard (NAAQS). Thus, very limited continuous measurements are available for PAHs, which would hinder the understanding of long-term pollution characteristics of PAHs in context of rapid development of economy and intensive urbanization in China. To investigate annual variation and its causes of airborne particulate-associated PAHs, a total of 18 PAHs (including 16 USEPA priority species) in PM10 and PM2.5 were measured in Beijing, the capital and one of megacities of China, for a decade (from the year of 2004 to 2013) with meteorological data simultaneously recorded. The long-term measurements of PAHs showed significant annual and seasonal variations for the total concentration of PAHs (ΣPAH18) and individual PAH species. The ΣPAH18 in PM10 was highest in 2010 and lowest in 2006. Likewise, the ΣPAH18 in PM2.5 reached the highest level in 2010 and dropped to the lowest level in 2005. The annual concentration varied insignificantly for 2- and 3-ring PAHs, were relatively high in the year of 2004, 2007 and 2010 for 4-ring PAHs, and increased gradually with year for 5- to 7-ring PAHs, the markers of motor vehicle emission. As for seasonal variation, the concentrations in winter (heating period) was higher than those in summer, while concentrations in spring and autumn ranked in the middle. As for BaP, one of criteria pollutants, its concentration exceeded NAAQS of China in winter. Source apportionment by factor analysis suggested the contributions of coal combustion, vehicle emissions, fugitive dust and straw burning. Especially, the great contributions of coal combustion and vehicle emission were also supported by diagnostic ratios. The backward trajectories showed air mass crossing polluted cities and transporting in low atmospheric boundary layer (ABL) along with local stagnant condition would lead to severe pollution of PAHs at the study area. Correlation analysis between the concentrations of PAHs with socio-economic status (SES) indicated the significant impacts of population, vehicle fleet and Gross Domestic Products (GDP). With growing vehicle fleet and GDP (indicating ecomonic development) and increasing population (indicating urbanization level), the ΣPAH18 showed an increasing tendency. In the decade covered by the study, China has been optimizing energy structure and implementing policy encouraging more efficient energy use. The remarkable improvement of air quality by the policies, with the data collected in this study, would unfortunatley not be noticed in a short period but could be expected in long-term. Key Words: Polycyclic Aromatic Hydrocarbons; Airborne Particulate Matter; Annual Variation; Source; Socioeconomic status; Beijing Acknowledgments: The study has been supported by Beijing Excellent Talents Project of the year of 2012 (No. 2012D009051000001) and by National Science Foundation (No.41175102)

Retardation effect of nitrogen compounds and condensed aromatics on shale oil catalytic cracking processing and their characterization.

PubMed

Li, Nan; Chen, Chen; Wang, Bin; Li, Shaojie; Yang, Chaohe; Chen, Xiaobo

Untreated shale oil, shale oil treated with HCl aqueous solution and shale oil treated with HCl and furfural were used to do comparative experiments in fixed bed reactors. Nitrogen compounds and condensed aromatics extracted by HCl and furfural were characterized by electrospray ionization Fourier transform cyclotron resonance mass spectrometry and gas chromatography and mass spectrometry, respectively. Compared with untreated shale oil, the conversion and yield of liquid products increased considerably after removing basic nitrogen compounds by HCl extraction. Furthermore, after removing nitrogen compounds and condensed aromatics by both HCl and furfural, the conversion and yield of liquid products further increased. In addition, N 1 class species are predominant in both basic and non-basic nitrogen compounds, and they are probably indole, carbazole, cycloalkyl-carbazole, pyridine and cycloalkyl-pyridine. As for the condensed aromatics, most of them possess aromatic rings with two to three rings and zero to four carbon atom.

Elements and polycyclic aromatic hydrocarbons in exhaust particles emitted by light-duty vehicles.

PubMed

Alves, Célia A; Barbosa, Cátia; Rocha, Sónia; Calvo, Ana; Nunes, Teresa; Cerqueira, Mário; Pio, Casimiro; Karanasiou, Angeliki; Querol, Xavier

2015-08-01

The main purpose of this work was to evaluate the chemical composition of particulate matter (PM) emitted by eight different light-duty vehicles. Exhaust samples from petrol and diesel cars (Euro 3 to Euro 5) were collected in a chassis dynamometer facility. To simulate the real-world driving conditions, three ARTEMIS cycles were followed: road, to simulate a fluid traffic flow and urban with hot and cold starts, to simulate driving conditions in cities. Samples were analysed for the water-soluble ions, for the elemental composition and for polycyclic aromatic hydrocarbons (PAHs), respectively, by ion chromatography, inductively coupled plasma atomic emission spectroscopy (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and gas chromatography-mass spectrometry (GC-MS). Nitrate and phosphate were the major water-soluble ions in the exhaust particles emitted from diesel and petrol vehicles, respectively. The amount of material emitted is affected by the vehicle age. For vehicles ≥Euro 4, most elements were below the detection limits. Sodium, with emission factors in the ranges 23.5-62.4 and 78.2-227μg km(-1), for petrol and diesel Euro 3 vehicles, respectively, was the major element. The emission factors of metallic elements indicated that diesel vehicles release three to five times more than petrol automobiles. Element emissions under urban cycles are higher than those found for on-road driving, being three or four times higher, for petrol vehicles, and two or three times, for diesel vehicles. The difference between cycles is mainly due to the high emissions for the urban cycle with hot start-up. As registered for elements, most of the PAH emissions for vehicles ≥Euro 4 were also below the detection limits. Regardless of the vehicle models or driving cycles, the two- to four-ring PAHs were always dominant. Naphthalene, with emission factors up to 925 μg km(-1), was always the most abundant PAH. The relative cancer risk associated with naphthalene was estimated to be up to several orders of magnitude higher than any of the chemical species found in the PM phase. The highest PAH emission factors were registered for diesel-powered vehicles. The condition of the vehicle can exert a decisive influence on both element and PAH emissions.

Distribution of polycyclic aromatic hydrocarbons in lime spray dryer ash

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

Ping Sun; Panuwat Taerakul; Linda K. Weavers

Four lime spray dryer (LSD) ash samples were collected from a spreader stoker boiler and measured for their concentrations of 16 U.S. EPA specified polycyclic aromatic hydrocarbons (PAHs). Results showed that the total measured PAH concentration correlated with the organic carbon content of the LSD ash. Each LSD ash sample was then separated using a 140 mesh sieve into two fractions: a carbon-enriched fraction ({gt}140 mesh) and a lime-enriched fraction ({lt}140 mesh). Unburned carbon was further separated from the carbon-enriched fraction with a lithiumheteropolytungstate (LST) solution. PAH measurements on these different fractions showed that unburned carbon had the highest PAHmore » concentrations followed by the carbon-enriched fraction, indicating that PAHs were primarily associated with the carbonaceous material in LSD ash. However, detectable levels of PAHs were also found in the lime-enriched fraction, suggesting that the fine spray of slaked lime may sorb PAH compounds from the flue gas in the LSD process. 37 refs., 5 figs., 4 tabs.« less

Chemometric techniques in distribution, characterisation and source apportionment of polycyclic aromatic hydrocarbons (PAHS) in aquaculture sediments in Malaysia.

PubMed

Retnam, Ananthy; Zakaria, Mohamad Pauzi; Juahir, Hafizan; Aris, Ahmad Zaharin; Zali, Munirah Abdul; Kasim, Mohd Fadhil

2013-04-15

This study investigated polycyclic aromatic hydrocarbons (PAHs) pollution in surface sediments within aquaculture areas in Peninsular Malaysia using chemometric techniques, forensics and univariate methods. The samples were analysed using soxhlet extraction, silica gel column clean-up and gas chromatography mass spectrometry. The total PAH concentrations ranged from 20 to 1841 ng/g with a mean of 363 ng/g dw. The application of chemometric techniques enabled clustering and discrimination of the aquaculture sediments into four groups according to the contamination levels. A combination of chemometric and molecular indices was used to identify the sources of PAHs, which could be attributed to vehicle emissions, oil combustion and biomass combustion. Source apportionment using absolute principle component scores-multiple linear regression showed that the main sources of PAHs are vehicle emissions 54%, oil 37% and biomass combustion 9%. Land-based pollution from vehicle emissions is the predominant contributor of PAHs in the aquaculture sediments of Peninsular Malaysia. Copyright © 2013 Elsevier Ltd. All rights reserved.

Assessment and source identification of pollution risk for touristic ports: Heavy metals and polycyclic aromatic hydrocarbons in sediments of 4 marinas of the Apulia region (Italy).

PubMed

Mali, Matilda; Dell'Anna, Maria Michela; Mastrorilli, Piero; Damiani, Leonardo; Piccinni, Alberto Ferruccio

2017-01-30

The Apulia region in Italy has the longest Adriatic coastline; thus, maritime tourism is the driving force for its economic development. Pollution risk for four representative touristic ports of the region was assessed by determining the concentrations of 10 metals, 16 polycyclic aromatic hydrocarbons (PAHs) congeners, and the main nutrients. The cumulative mean Effects Range-Median quotient (mERMq) was used to assess the hazard degree, while the distribution patterns and content ratios of different PAH sediment concentrations were investigated to identify the pollution sources. Principal component analyses indicated an anomalous pollution trend for one of the small touristic ports assessed; this trend emerged from contamination by heavy metals and PAHs to a larger extent than expected, considering the main activity in this port, especially in its inner basin. The reason of this anomaly is thought to be the hydrodynamic and/or other stress factors. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of pyrolysis temperatures on freely dissolved polycyclic aromatic hydrocarbon (PAH) concentrations in sewage sludge-derived biochars.

PubMed

Zielińska, Anna; Oleszczuk, Patryk

2016-06-01

The aim of this study was to evaluate the effect of sewage sludge pyrolysis on freely dissolved (Cfree) polycyclic aromatic hydrocarbon (PAH) contents in biochars. Four sewage sludges with varying properties and PAH contents were pyrolysed at temperatures of 500 °C, 600 °C or 700 °C. Cfree PAH contents were determined using polyoxymethylene (POM). The contents of Cfree PAHs in the sludges ranged from 262 to 294 ng L(-1). Sewage sludge-derived biochars have from 2.3- to 3.4-times lower Cfree PAH contents comparing to corresponding sewage sludges. The Cfree PAH contents in the biochars ranged between 81 ng L(-1) and 126 ng L(-1). As regards agricultural use of biochar, the lower contents of Cfree PAHs in the biochars compared to the sewage sludges makes biochar a safer material than sewage sludge in terms of PAH contents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Investigation of the Reactions and Distribution of Polycyclic Aromatic Hydrocarbons and Fullerenes in Extraterrestrial Material

NASA Technical Reports Server (NTRS)

Zare, Richard N.

2005-01-01

The work funded by this research grant includes four specific projects: (1) Mapping the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. (2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe laser-desorption laser-ionization mass spectrometry ( pL2MS) and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. (3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. (4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames.

Generalised Multiplicative Indices of Polycyclic Aromatic Hydrocarbons and Benzenoid Systems

NASA Astrophysics Data System (ADS)

Kulli, V. R.; Stone, Branden; Wang, Shaohui; Wei, Bing

2017-05-01

Many types of topological indices such as degree-based topological indices, distance-based topological indices, and counting-related topological indices are explored during past recent years. Among degree-based topological indices, Zagreb indices are the oldest one and studied well. In the paper, we define a generalised multiplicative version of these indices and compute exact formulas for Polycyclic Aromatic Hydrocarbons and jagged-rectangle Benzenoid systems.

A thermodynamic analysis of the environmental indicators of natural gas combustion processes

NASA Astrophysics Data System (ADS)

Elsukov, V. K.

2010-07-01

Environmental indicators of the natural gas combustion process are studied using the model of extreme intermediate states developed at the Melent’ev Institute of Power Engineering Systems. Technological factors responsible for generation of polycyclic aromatic hydrocarbons and hydrogen cyanide are revealed. Measures for reducing the amounts of polycyclic aromatic hydrocarbons, hydrogen cyanide, nitrogen oxide, and other pollutants emitted from boilers are developed.

New SERS Substrates For Polycyclic Aromatic Hydrocarbon (PAH) Detection: Towards Quantitative SERS Sensors For Environmental Analysis

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

Peron, O.; Laboratoire de Nanotechnologie et d'instrumentation Optique, Institut Charles Delaunay, FRE 2848, Universite de technologie de Troyes, 12 rue Marie Curie, 10010 Troyes; Rinnert, E.

2010-08-06

In the investigation of chemical pollutions, such as PAHs (Polycyclic Aromatic Hydrocarbons) at low concentration in aqueous medium, surface-enhanced Raman scattering (SERS) stands for an alternative to the inherent low cross-section of normal Raman scattering. Indeed, SERS is a very sensitive spectroscopic technique due to the excitation of the surface plasmon modes of the nanostructured metallic film.

EXPLORING RELATIONSHIPS BETWEEN OUTDOOR AIR PARTICULATE-ASSOCIATED POLYCYCLIC AROMATIC HYDROCARBON AND PM2.5: A CASE STUDY OF BENZO(A)PYRENE IN CALIFORNIA METROPOLITAN REGIONS

EPA Science Inventory

Polycyclic aromatic hydrocarbons (PAHs) and particulate matter (PM) are co-pollutants emitted as by-products of combustion processes. Convincing evidence exists for PAHs as a primary toxic component of fine PM (PM_2.5). Because PM_2.5 is listed by the US EPA a...

A NOVEL METABOLIC ACTIVATION PATHWAY FOR POLYCYCLIC AROMATIC HYDROCARBONS: REACTIVE OXYGEN SPECIES-MEDIATED DNA DAMAGE AND MORPHOLOGICAL CELL TRANSFORMATION IN MOUSE EMBRYO CELLS BY K-REGION DIOL METABOLITES

EPA Science Inventory

Benzo[ a ]pyrene (BP) is a well-studied polycyclic aromatic hydrocarbon (P AH) .Many
mechanisms have been suggested to explain its carcinogenic activity, yet many questions still
remain. K-region dihydrodiols (diols) ofPAHs are common metabolites and some are genotoxic. W...

Combined effects of prenatal polycyclic aromatic hydrocarbons and material hardship on child IQ.

PubMed

Vishnevetsky, Julia; Tang, Deliang; Chang, Hsin-Wen; Roen, Emily L; Wang, Ya; Rauh, Virginia; Wang, Shuang; Miller, Rachel L; Herbstman, Julie; Perera, Frederica P

2015-01-01

Polycyclic aromatic hydrocarbons are common carcinogenic and neurotoxic urban air pollutants. Toxic exposures, including air pollution, are disproportionately high in communities of color and frequently co-occur with chronic economic deprivation. We examined whether the association between child IQ and prenatal exposure to polycyclic aromatic hydrocarbons differed between groups of children whose mothers reported high vs. low material hardship during their pregnancy and through child age 5. We tested statistical interactions between hardships and polycyclic aromatic hydrocarbons, as measured by DNA adducts in cord blood, to determine whether material hardship exacerbated the association between adducts and IQ scores. Prospective cohort. Participants were recruited from 1998 to 2006 and followed from gestation through age 7 years. Urban community (New York City) A community-based sample of 276 minority urban youth EXPOSURE MEASURE: Polycyclic aromatic hydrocarbon-DNA adducts in cord blood as an individual biomarker of prenatal polycyclic aromatic hydrocarbon exposure. Maternal material hardship self-reported prenatally and at multiple timepoints through early childhood. Child IQ at 7 years assessed using the Wechsler Intelligence Scale for Children. Significant inverse effects of high cord PAH-DNA adducts on full scale IQ, perceptual reasoning and working memory scores were observed in the groups whose mothers reported a high level of material hardship during pregnancy or recurring high hardship into the child's early years, and not in those without reported high hardship. Significant interactions were observed between high cord adducts and prenatal hardship on working memory scores (β = -8.07, 95% CI (-14.48, -1.66)) and between high cord adducts and recurrent material hardship (β = -9.82, 95% CI (-16.22, -3.42)). The findings add to other evidence that socioeconomic disadvantage can increase the adverse effects of toxic physical "stressors" like air pollutants. Observed associations between high cord adducts and reduced IQ were significant only among the group of children whose mothers reported high material hardship. These results indicate the need for a multifaceted approach to prevention. Copyright © 2015 Elsevier Inc. All rights reserved.

Microplastics and polycyclic aromatic hydrocarbons (PAHs) in Xiamen coastal areas: Implications for anthropogenic impacts.

PubMed

Tang, Guowen; Liu, Mengyang; Zhou, Qian; He, Haixia; Chen, Kai; Zhang, Haibo; Hu, Jiahui; Huang, Qinghui; Luo, Yongming; Ke, Hongwei; Chen, Bin; Xu, Xiangrong; Cai, Minggang

2018-09-01

Microplastics and polycyclic aromatic hydrocarbons (PAHs) were investigated to study the influence of human activities and to find their possible relationship on the coastal environments, where the coastal areas around Xiamen are undergoing intensive processes of industrialization and urbanization in the southeast China. The abundance of microplastics in Xiamen coastal areas was 103 to 2017particles/m 3 in surface seawater and 76 to 333 particles/kg in sediments. Concentrations of dissolved PAHs varied from 18.1 to 248ng/L in surface seawater. The abundances of microplastics from the Western Harbor in surface seawater and sediments were higher than those from other areas. Foams were dominated in surface seawater samples, however, no foams were found in sediments samples. The microscope selection and FTIR analysis suggested that polyethylene (PE) and polypropylene (PP) were dominant microplastics. The cluster analysis results demonstrated that fibers and granules had the similar sources, and films had considerably correlation with all types of PAHs (3 or 4-ring PAHs and alkylated PAHs). Plastic film mulch from agriculture practice might be a potential source of microplastics in study areas. Results of our study support that river runoff, watershed area, population and urbanization rate influence the distribution of microplastics in estuarine surface water, and the prevalence of microplastic pollution calls for monitoring microplastics at a national scale. Copyright © 2018 Elsevier B.V. All rights reserved.

Application of aqueous saponin on the remediation of polycyclic aromatic hydrocarbons-contaminated soil.

PubMed

Kobayashi, Takayuki; Kaminaga, Hirohisa; Navarro, Ronald R; Iimura, Yosuke

2012-01-01

The aim of this research was to evaluate the feasibility of aqueous saponin for the removal and biodegradation of polycyclic aromatic hydrocarbons (PAHs) from contaminated soil. Dissolution test confirmed the ability of saponin to increase the apparent solubility of the tested 3-5 rings PAH above the critical micelle concentration (approximately 1000 mg/L). Microbial test with pure culture of Sphingomonas sp. showed that saponin significantly enhanced the degradation of pyrene. For example, the percent degradation was 2.1 times higher in the presence of 2500 mg/L saponin than that of control without saponin after 60 hours incubation at around 10(8) CFU/mL initial cell loading. These results suggest that the binding of pyrene with saponin does not pose a serious constraint to bacterial uptake. Contrary to pyrene, saponin was chemically stable against the PAHs degrader. It is also not toxic to the cell at least up to 2500 mg/L. Finally, using a spiked soil sample, extraction tests with 10,000 mg/L of saponin showed that around 52.7% and 0.3% of pyrene was removed from low and high organic spiked soils, respectively. The results from this study indicate that aqueous saponin is appropriate as a washing agent as well as biodegradation enhancer for the detoxification of PAHs-contaminated low organic carbon soil.

Polycyclic Aromatic Hydrocarbons (PAHs) in Indoor Dusts of Guizhou, Southwest of China: Status, Sources and Potential Human Health Risk

PubMed Central

Li, Baizhan

2015-01-01

Polycyclic aromatic hydrocarbons (PAHs) were analyzed for 136 indoor dust samples collected from Guizhou province, southwest of China. The ∑18PAHs concentrations ranged from 2.18 μg•g-1 to 14.20 μg•g-1 with the mean value of 6.78 μg•g-1. The highest Σ18PAHs concentration was found in dust samples from orefields, followed by city, town and village. Moreover, the mean concentration of Σ18PAHs in indoor dust was at least 10% higher than that of outdoors. The 4–6 rings PAHs, contributing more than 70% of ∑18PAHs, were the dominant species. PAHs ratios, principal component analysis with multiple linear regression (PCA-MLR) and hierarchical clustering analysis (HCA) were applied to evaluate the possible sources. Two major origins of PAHs in indoor dust were identified as vehicle emissions and coal combustion. The mean incremental lifetime cancer risk (ILCR) due to human exposure to indoor dust PAHs in city, town, village and orefield of Guizhou province, China was 6.14×10−6, 5.00×10−6, 3.08×10−6, 6.02×10−6 for children and 5.92×10−6, 4.83×10−6, 2.97×10−6, 5.81×10−6 for adults, respectively. PMID:25719362

Receptor modelling study of polycyclic aromatic hydrocarbons in Jeddah, Saudi Arabia.

PubMed

Alghamdi, Mansour A; Alam, Mohammed S; Yin, Jianxin; Stark, Christopher; Jang, Eunhwa; Harrison, Roy M; Shamy, Magdy; Khoder, Mamdouh I; Shabbaj, Ibrahim I

2015-02-15

Measurements of 14 polycyclic aromatic hydrocarbons (PAH) have been made in Jeddah, Saudi Arabia, with a view to establishing the concentrations in this major city, and quantifying the contributions of major sources. Particulate and vapour forms have been sampled and analysed separately. The concentrations are compared to measurements from other sites in the Middle Eastern region and are towards the lower end of the range, being far lower than concentrations reported from Riyadh (Saudi Arabia), Assiut (Egypt) and Tehran (Iran) but broadly similar to those measured in Damascus (Syria) and higher than those measured in Kuwait. The partitioning between vapour and particle phases is similar to that in data from Egypt and China, but with many compounds showing a higher particle-associated percentage than in Birmingham (UK) possibly reflecting a higher concentration of airborne particulate matter in the former countries. Concentrations in Jeddah were significantly higher at a site close to the oil refinery and a site close to a major ring road than at a suburban site to the north of the city. Application of positive matrix factorisation to the pooled data elicited three factors accounting respectively for 17%, 33% and 50% of the measured sum of PAH and these are interpreted as arising from gasoline vehicles, industrial sources, particularly the oil refinery, and to diesel/fuel oil combustion. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Polycyclic aromatic hydrocarbons in sediments and marine organisms: Implications of anthropogenic effects on the coastal environment.

PubMed

Sun, Runxia; Sun, Yue; Li, Qing X; Zheng, Xiaobo; Luo, Xiaojun; Mai, Bixian

2018-05-30

Intensive human activities aggravate environmental pollution, particularly in the coastal environment. Sixteen priority polycyclic aromatic hydrocarbons (PAHs) were determined in the sediments and marine species from Zhanjiang Harbor, a large harbor in China. The total PAH concentrations ranged from 151 to 453 ng/g dry weight (dw) in sediments and from 86.7 to 256 ng/g wet weight (ww) in organism tissues. High levels of PAHs occurred in the sample sites next to the estuary. A decrease in PAH levels was observed in comparison to the previous survey prior to 2012. Fish exhibited lower lipid weight normalized PAH concentrations than the other species, which may be related to their efficient metabolic transformation. Three ring PAHs dominated both in marine sediments and species, but low molecular weight PAHs exhibited higher proportions in biota than in sediments (p < 0.05). Petrogenic and pyrolytic sources both contributed to the occurrence of PAHs, and the latter became increasingly important in the study area. The ecological risk from PAHs in the sediments was relatively low (9% incidence of adverse biological effect) according to the effects-based sediment quality guideline values. Exposure to PAHs via consuming seafoods might pose a health risk to local residents. Overall, these results revealed anthropogenic activities in the coastal area have an impact on the local ecosystem. Copyright © 2018 Elsevier B.V. All rights reserved.

Reconstruction of metabolic networks in a fluoranthene-degrading enrichments from polycyclic aromatic hydrocarbon polluted soil.

PubMed

Zhao, Jian-Kang; Li, Xiao-Ming; Ai, Guo-Min; Deng, Ye; Liu, Shuang-Jiang; Jiang, Cheng-Ying

2016-11-15

Microbial degradation of polycyclic aromatic hydrocarbons (PAHs) is the primary process of removing PAHs from environments. The metabolic pathway of PAHs in pure cultures has been intensively studied, but cooperative metabolisms at community-level remained to be explored. In this study, we determined the dynamic composition of a microbial community and its metabolic intermediates during fluoranthene degradation using high-throughput metagenomics and gas chromatography-mass spectrometry (GC-MS), respectively. Subsequently, a cooperative metabolic network for fluoranthene degradation was constructed. The network shows that Mycobacterium contributed the majority of ring-hydroxylating and -cleavage dioxygenases, while Diaphorobacter contributed most of the dehydrogenases. Hyphomicrobium, Agrobacterium, and Sphingopyxis contributed to genes encoding enzymes involved in downstream reactions of fluoranthene degradation. The contributions of various microbial groups were calculated with the PICRUSt program. The contributions of Hyphomicrobium to alcohol dehydrogenases were 62.4% in stage 1 (i.e., when fluoranthene was rapidly removed) and 76.8% in stage 3 (i.e., when fluoranthene was not detectable), respectively; the contribution of Pseudomonas were 6.6% in stage 1 and decreased to 1.2% in subsequent stages. To the best of the author's knowledge, this report describes the first cooperative metabolic network to predict the contributions of various microbial groups during PAH-degradation at community-level. Copyright © 2016 Elsevier B.V. All rights reserved.

Variation of polycyclic aromatic hydrocarbons in atmospheric PM2.5 during winter haze period around 2014 Chinese Spring Festival at Nanjing: Insights of source changes, air mass direction and firework particle injection.

PubMed

Kong, Shaofei; Li, Xuxu; Li, Li; Yin, Yan; Chen, Kui; Yuan, Liang; Zhang, Yingjie; Shan, Yunpeng; Ji, Yaqin

2015-07-01

Daily PM2.5 samples were collected at a suburban site of Nanjing around 2014 Chinese Spring Festival (SF) and analyzed for 18 kinds of polycyclic aromatic hydrocarbons (PAHs) by GC-MS. Comparison of PAH concentrations during different periods, with different air mass origins and under different pollution situations was done. Sources were analyzed by diagnostics ratios and principal component analysis (PCA). The threat of PAHs was assessed by BaP equivalent concentrations (BaPeq) and incremental lifetime cancer risk (ILCR). The averaged PAHs for pre-SF, SF and after SF periods were 50.6, 17.2 and 29 ng m(-3), indicating the variations of PAH sources, with reduced traffic, industrial and construction activities during SF and gradually re-starting of them after-SF. According to PAH mass concentrations, their relative abundance to particles, ratio of PAHs (3-ring+4-ring)/PAHs(5-ring+6-ring), mass concentrations of combustion-derived and carcinogenic PAHs, fireworks burning is an important source for PAHs during SF. The ILCR values for Chinese New Year day were 0.68 and 3.3 per 100,000 exposed children and adults. It suggested the necessity of controlling fireworks burning during Chinese SF period which was always companied with serious regional haze pollution. PAH concentrations exhibited decreasing trend when air masses coming from the following directions as North China Plain (63.9 ng m(-3))>Central China (53.0 ng m(-3))>Shandong Peninsula (46.6 ng m(-3))>Northwest China (18.8 ng m(-3))>Sea (15.8 ng m(-3)). For different pollution situations, they decreased as haze (44.5 ng m(-3))>fog-haze (28.4 ng m(-3))>clear (12.2 ng m(-3))>fog day (9.2 ng m(-3)). Coal combustion, traffic emission, industrial processes and petroleum (only for non-SF holiday periodss) were the main sources of PM2.5 associated PAHs. Fireworks burning contributed 14.0% of PAHs during SF period. Directly measurement of PAHs from fireworks burning is urgently needed for source apportionment studies in the future. Copyright © 2015 Elsevier B.V. All rights reserved.

Cardiac toxicity of 5-ring polycyclic aromatic hydrocarbons is differentially dependent on the aryl hydrocarbon receptor 2 isoform during zebrafish development

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

Incardona, John P., E-mail: john.incardona@noaa.gov; Linbo, Tiffany L.; Scholz, Nathaniel L.

Petroleum-derived compounds, including polycyclic aromatic hydrocarbons (PAHs), commonly occur as complex mixtures in the environment. Recent studies using the zebrafish experimental model have shown that PAHs are toxic to the embryonic cardiovascular system, and that the severity and nature of this developmental cardiotoxicity varies by individual PAH. In the present study we characterize the toxicity of the relatively higher molecular weight 5-ring PAHs benzo[a]pyrene (BaP), benzo[e]pyrene (BeP), and benzo[k]fluoranthene (BkF). While all three compounds target the cardiovascular system, the underlying role of the ligand-activated aryl hydrocarbon receptor (AHR2) and the tissue-specific induction of the cytochrome p450 metabolic pathway (CYP1A) weremore » distinct for each. BaP exposure (40 {mu}M) produced AHR2-dependent bradycardia, pericardial edema, and myocardial CYP1A immunofluorescence. By contrast, BkF exposure (4-40 {mu}M) caused more severe pericardial edema, looping defects, and erythrocyte regurgitation through the atrioventricular valve that were AHR2-independent (i.e., absent myocardial or endocardial CYP1A induction). Lastly, exposure to BeP (40 {mu}M) yielded a low level of CYP1A+ signal in the vascular endothelium of the head and trunk, without evident toxic effects on cardiac function or morphogenesis. Combined with earlier work on 3- and 4-ring PAHs, our findings provide a more complete picture of how individual PAHs may drive the cardiotoxicity of mixtures in which they predominate. This will improve toxic injury assessments and risk assessments for wild fish populations that spawn in habitats altered by overlapping petroleum-related human impacts such as oil spills, urban stormwater runoff, or sediments contaminated by legacy industrial activities. -- Highlights: Black-Right-Pointing-Pointer PAH compounds with 5 rings in different arrangements caused differential tissue-specific patterns of CYP1A induction in zebrafish embryos. Black-Right-Pointing-Pointer These compounds produced differential cardiac developmental toxicity that did not strictly correlate with associated CYP1A induction. Black-Right-Pointing-Pointer Cardiotoxicity of benzo(a)pyrene was partially dependent on the AHR2 isoform, while benzo(k)fluoranthene cardiotoxicity was not. Black-Right-Pointing-Pointer Individual PAH compounds have distinct toxicokinetic pathways in fish embryos, and act through different toxic mechanisms.« less

Ecological Uptake and Depuration of Carbon Nanotubes by Lumbriculus variegatus

PubMed Central

Petersen, Elijah J.; Huang, Qingguo; Weber, Walter J.

2008-01-01

Background Carbon nanotubes represent a class of nanomaterials having broad application potentials and documented cellular uptake and ecotoxicological effects that raise the possibility that they may bioaccumulate in living organisms. Objectives Radioactively labeled nanotubes were synthesized using a novel methane chemical vapor deposition procedure. Single-walled carbon nanotubes (SWNTs), multiwalled carbon nanotubes (MWNTs), and pyrene were spiked to sediment samples, and the respective uptake and depuration of these nanotubes and pyrene were assessed by the oligochaete, Lumbriculus variegatus. Results 14C-labeled carbon nanotubes were developed for these experiments to overcome significant previous limitations for quantifying nanotube materials in environmental and biological media. Biota-sediment accumulation factors for SWNTs and MWNTs were observed to be almost an order of magnitude lower than those for pyrene, a four-ringed polycyclic aromatic hydrocarbon (PAH). The depuration behaviors of the oligochaete suggested that the nanotubes detected in these organisms were associated with sediments remaining in the organism guts and not absorbed into cellular tissues as was the pyrene. The results suggest that, unlike PAHs, purified carbon nanotubes do not readily absorb into organism tissues. PMID:18414633

Application of response surface methodology for rapid chrysene biodegradation by newly isolated marine-derived fungus Cochliobolus lunatus strain CHR4D.

PubMed

Bhatt, Jwalant K; Ghevariya, Chirag M; Dudhagara, Dushyant R; Rajpara, Rahul K; Dave, Bharti P

2014-11-01

For the first time, Cochliobolus lunatus strain CHR4D, a marine-derived ascomycete fungus isolated from historically contaminated crude oil polluted shoreline of Alang-Sosiya ship-breaking yard, at Bhavnagar coast, Gujarat has been reported showing the rapid and enhanced biodegradation of chrysene, a four ringed high molecular weight (HMW) polycyclic aromatic hydrocarbon (PAH). Mineral Salt Broth (MSB) components such as ammonium tartrate and glucose along with chrysene, pH and trace metal solution have been successfully optimized by Response Surface Methodology (RSM) using central composite design (CCD). A validated, two-step optimization protocol has yielded a substantial 93.10% chrysene degradation on the 4(th) day, against unoptimized 56.37% degradation on the 14(th) day. The results depict 1.65 fold increase in chrysene degradation and 1.40 fold increase in biomass with a considerable decrement in time. Based on the successful laboratory experiments, C. lunatus strain CHR4D can thus be predicted as a potential candidate for mycoremediation of HMW PAHs impacted environments.

Health risk assessment and source study of PAHs from roadside soil dust of a heavy mining area in India.

PubMed

Tarafdar, Abhrajyoti; Sinha, Alok

2018-02-26

The total concentrations of 13 detected polycyclic aromatic hydrocarbons (PAHs) in different traffic soil samples of Dhanbad heavy mining area, India, were between 8.256 and 12.562 µg/g and were dominated by four ring PAHs (44%). Diagnostic ratio study revealed that fossil fuel burning and vehicular pollution are the most prominent sources of the PAHs in roadside soil even at a heavy coal mining area. The 90th percentiles cancer risks determined by probabilistic health risk assessment (Monte Carlo simulations) for both the age groups (children and adults) were above tolerable limit (>1.00E-06) according to USEPA. The simulated mean cancer risk was 1.854E-05 for children and 1.823E-05 for adults. For different exposure pathways, dermal contact was observed to be the major pathway with an exposure load of 74% for children and 85% for adults. Sensitivity analysis demonstrated relative skin adherence factor for soil (AF) is the most influential parameter of the simulation, followed by exposure duration (ED).

Occupational syncarcinogenesis in the skin - combined effects of two carcinogens from the German occupational disease list.

PubMed

Dickel, Heinrich; Blome, Otto; Dickel, Beate; Bruckner, Thomas; Stockfleth, Eggert; Soemantri, Silas Paras

2016-12-01

Though scientifically undisputed, cutaneous syncarcinogenesis is not reflected in German occupational disease (OD) regulations, which tend to be guided by the tenet of monocausality. Recognition of nonmelanoma skin cancer (NMSC) and its precursor lesions as OD requires individual assessment as to whether the requirements pursuant to either OD 5103 (occupational exposure to natural UV radiation) or OD 5102 (occupational exposure to polycyclic aromatic hydrocarbons) are fulfilled. Retrospective analysis of 28 patients (median age 72.5 years) with NMSC and respective precursor lesions who had been occupationally exposed to natural UV radiation and polycyclic aromatic hydrocarbons. All cases had undergone expert medical assessment between September 2012 and September 2015. According to our assessments, all 28 cases met the occupational requirements pursuant to OD 5103 and 5102. In 26 cases (93 %), we recommended recognition of skin cancer as occupational disease pursuant to both OD 5103 and OD 5102. The competent occupational insurance association (BG) followed our recommendation in four cases. In eight cases, recognition was solely based on OD 5103; in ten cases, only on OD 5102. Four cases were denied recognition. Following adequate cumulative occupational exposure to natural UV light as well as occupational exposure to polycyclic aromatic hydrocarbons, NMSC or its precursor lesions arising in UV-exposed areas should be reported to the competent occupational insurance association as "OD 5103 and 5102 in terms of syncarcinogenesis". Apart from the fact that the ensuing recognition proceedings will be able to more adequately reflect real-life workplace conditions, filing a report pursuant to both ODs also allows for recognition of basal cell carcinoma as occupational disease. According to current regulations, this would not be possible, if the assessment were solely based on OD 5103. © 2016 Deutsche Dermatologische Gesellschaft (DDG). Published by John Wiley & Sons Ltd.

Oxidation of polycyclic aromatic hydrocarbons under sulfate-reducing conditions

USGS Publications Warehouse

Coates, J.D.; Anderson, R.T.; Lovley, D.R.

1996-01-01

[14C]naphthalene and phenanthrene were oxidized to 14CO2 without a detectable lag under strict anaerobic conditions in sediments from San Diego Bay, San Diego, Calif., that were heavily contaminated with polycyclic aromatic hydrocarbons (PAHs) but not in less contaminated sediments. Sulfate reduction was necessary for PAH oxidation. These results suggest that the self-purification capacity of PAH-contaminated sulfate-reducing environments may be greater than previously recognized.

Synthesis of g-C3N4/Fe3O4 nanocomposites and application as a new sorbent for solid phase extraction of polycyclic aromatic hydrocarbons in water samples.

PubMed

Wang, Man; Cui, Shihai; Yang, Xiaodi; Bi, Wentao

2015-01-01

An easy preparation of g-C3N4/Fe3O4 nanocomposites by chemical co-precipitation has been demonstrated. The as-prepared materials were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. The high affinity of g-C3N4 toward polycyclic aromatic hydrocarbons and the magnetic behavior of Fe3O4 were combined to provide an efficient and simple magnetic solid phase extraction (MSPE). The adsorption and desorption of polycyclic aromatic hydrocarbons on g-C3N4/Fe3O4 were examined. Different factors affecting the magnetic solid phase extraction of polycyclic aromatic hydrocarbons were assessed in terms of adsorption, desorption, and recovery. Under the optimized conditions, the proposed method showed good limits of detection (LOD, S/N=3) in the range of 0.05-0.1 ng mL(-1) and precision in the range of 1.8-5.3% (RSDs, n=3). This method was also successfully applied to the analysis of real water samples; good spiked recoveries over the range of 80.0-99.8% were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Polyaniline-coated cigarette filters as a solid-phase extraction sorbent for the extraction and enrichment of polycyclic aromatic hydrocarbon in water samples.

PubMed

Bunkoed, Opas; Rueankaew, Thanaschaphorn; Nurerk, Piyaluk; Kanatharana, Proespichaya

2016-06-01

Polyaniline coated cigarette filters were successfully synthesized and used as a solid-phase extraction sorbent for the extraction and preconcentration of polycyclic aromatic hydrocarbons in water samples. The polyaniline helped to enhance the adsorption ability of polycyclic aromatic hydrocarbons on the sorbent through π-π interactions. The high porosity and large surface area of the cigarette filters helped to reduce backpressure and can be operated with high sample flow rate without loss of extraction efficiency. The developed sorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The parameters that affected the extraction efficiencies, i.e. polymerization time, type of desorption solvent and its volume, sample flow rate, sample volume, sample pH, ionic strength, and organic modifier were investigated. Under the optimal conditions, the method was linear over the range of 0.5-10 μg/L and a detection limit of 0.5 ng/L. This simple, rapid, and cost-effective method was successfully applied to the preconcentration of polycyclic aromatic hydrocarbons from water samples. The developed method provided a high enrichment factor with good extraction efficiency (85-98%) and a relative standard deviation <10%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory evidence for ionized polycyclic aromatic hydrocarbons in the interstellar medium

NASA Technical Reports Server (NTRS)

Szczepanski, Jan; Vala, Martin

1993-01-01

The infrared absorption from neutrals and cations of four PAHs - naphthalene, anthracene, pyrene, and perylene - integrated over the spectral regions corresponding to the interstellar bands are compared with astronomical observations. It is found that the interstellar bands cannot be explained solely on the basis of neutral PAH species, but that cations must be a significant, and in some cases dominant, component.

25 years monitoring of PAHs and petroleum hydrocarbons biodegradation in soil.

PubMed

Harmsen, Joop; Rietra, René P J J

2018-05-10

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) and total petroleum hydrocarbons (TPH) in sediment and soil has been monitored on seven experimental fields during periods up to 25 years. With this unique dataset, we investigated long-term very slow biodegradation under field conditions. . The data show that three biodegradation rates can be distinguished for PAHs: 1) rapid degradation during the first year, 2) slow degradation during the following 6 years and 3), subject of this paper, a very slow degradation after 7 years until at least 25 years. Beside 2-, 3- and 4-ring PAHs, also 5- and 6-ring PAHs (aromatic rings) were degraded, all at the same rate during very slow degradation. In the period of very slow degradation, 6% yr -1 of the PAHs present were removed in five fields and 2% yr -1 in two other fields, while in the same period no very slow degradation of TPH could be observed. The remaining petroleum hydrocarbons were high boiling and non-toxic. Using the calculated degradation rates and the independently measured bioavailability of the PAHs (Tenax-method), the PAHs degradation curves of all seven monitored fields could be modelled. Applying the model and data obtained with the Tenax-method for fresh contaminated material, results of long-term biodegradation can be predicted, which can support the use of bioremediation in order to obtain a legally acceptable residual concentration. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Glutathione S-transferase-encoding gene as a potential probe for environmental bacterial isolates capable of degrading polycyclic aromatic hydrocarbons.

PubMed Central

Lloyd-Jones, G; Lau, P C

1997-01-01

Homologs of the glutathione S-transferase (GST)-encoding gene were identified in a collection of aromatic hydrocarbon-degrading Sphingomonas spp. isolated from New Zealand, Antarctica, and the United States by using PCR primers designed from the GST-encoding gene of Sphingomonas paucimobilis EPA505. Sequence analysis of PCR fragments generated from these isolates and of the GST gene amplified from DNA extracted from polycyclic aromatic hydrocarbon (PAH)-contaminated soil revealed a high degree of conservation, which may make the GST-encoding gene a potentially useful marker for PAH-degrading bacteria. PMID:9251217

The Study of Acenaphthene and its Complexation with Water

NASA Astrophysics Data System (ADS)

Steber, Amanda; Perez, Cristobal; Rijs, Anouk; Schnell, Melanie

2016-06-01

Acenaphthene (Ace) is a three ring polycyclic aromatic hydrocarbon (PAH), which consists of naphthalene and a non-aromatic five member ring. Ace has been previously been studied by microwave spectroscopy where the rotational constants were reported[1]. New measurements from 2-8 GHz using chirped pulse-Fourier transform microwave spectroscopy (CP-FTMW) will be presented. The high sensitivity achieved enabled us to observe all 13C isotopologues in natural abundance and determine the Kraitchman substitution structure. The spectra of Ace complexed with water and H218O were also recorded at this frequency range. From these spectra, we have been able to assign the complexes Ace-(H2O)n, n=1-3 and (Ace)2-H2O and experimentally derive the O-atom position of the H2O. The Ace-(H2O)3 complex is especially interesting as the water aggregate forms a slightly distorted cyclic water trimer from that observed in the IR[2]. These complexes could give insight about the formation of ice grains in the interstellar medium. [1] Thorwirth, S., Theulé, P., Gottlieb, C.A., McCarthy, M.C., Thaddeus, P. Astrophys. J., 662, 1309-1314, 2007. [2] Keutsch, F.N., Cruzan, J.D., Saykally, R.J. Chem. Rev., 103, 2533-2577, 2003.

Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

DOEpatents

Baker, Eddie G.; Elliott, Douglas C.

1993-01-01

The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compouns as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

Method of upgrading oils containing hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline

DOEpatents

Baker, E.G.; Elliott, D.C.

1993-01-19

The present invention is a multi-stepped method of converting an oil which is produced by various biomass and coal conversion processes and contains primarily single and multiple ring hydroxyaromatic hydrocarbon compounds to highly aromatic gasoline. The single and multiple ring hydroxyaromatic hydrocarbon compounds in a raw oil material are first deoxygenated to produce a deoxygenated oil material containing single and multiple ring aromatic compounds. Then, water is removed from the deoxygenated oil material. The next step is distillation to remove the single ring aromatic compounds as gasoline. In the third step, the multiple ring aromatics remaining in the deoxygenated oil material are cracked in the presence of hydrogen to produce a cracked oil material containing single ring aromatic compounds. Finally, the cracked oil material is then distilled to remove the single ring aromatics as gasoline.

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

PubMed

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

2013-03-01

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

Characteristics of PAHs from deep-frying and frying cooking fumes.

PubMed

Yao, Zhiliang; Li, Jing; Wu, Bobo; Hao, Xuewei; Yin, Yong; Jiang, Xi

2015-10-01

Cooking fumes are an important indoor source of polycyclic aromatic hydrocarbons (PAHs). Because indoor pollution has a more substantial impact on human health than outdoor pollution, PAHs from cooking fumes have drawn considerable attention. In this study, 16 PAHs emitted through deep-frying and frying methods using rapeseed, soybean, peanut, and olive oil were examined under a laboratory fume hood. Controlled experiments were conducted to collect gas- and particulate-phase PAHs emitted from the cooking oil fumes, and PAH concentrations were quantified via high-performance liquid chromatography (HPLC). The results show that deep-frying methods generate more PAHs and benzo[a]pyrene (B[a]P) (1.3 and 10.9 times, respectively) because they consume greater volumes of edible oil and involve higher oil temperatures relative to those of frying methods. In addition, the total B[a]Peq concentration of deep-frying is 2.2-fold larger than that of frying. Regarding the four types of edible oils studied, rapeseed oil produced more PAH emission than the other three oil varieties. For all of the cooking tests, three- and four-ringed PAHs were the main PAH components regardless of the food and oil used. Concerning the PAH partition between gas and particulate phase, the gaseous compounds accounted for 59-96 % of the total. Meanwhile, the particulate fraction was richer of high molecular weight PAHs (five-six rings). Deep-frying and frying were confirmed as important sources of PAH pollution in internal environments. The results of this study provide additional insights into the polluting features of PAHs produced via cooking activities in indoor environments.

Bioaccumulation of polycyclic aromatic compounds: 1. Bioconcentration in two marine species and in semipermeable membrane devices during chronic exposure to dispersed crude oil.

PubMed

Baussant, T; Sanni, S; Jonsson, G; Skadsheim, A; Børseth, J F

2001-06-01

Assessing the fate in marine biota of hydrocarbons derived from oil particles that are discharged during exploration and production is of relevant environmental concern. However, a rather complex experimental setup is required to carry out such investigations. In this study, a sophisticated tool, the continuous-flow system (CFS), was used to mimic dispersed oil exposure to marine biota. Polycyclic aromatic hydrocarbon (PAH) uptake was studied in two species, the blue mussel Mytilus edulis and juvenile of the turbot Scophthalmus maximus, and in semipermeable membrane devices (SPMD) exposed to crude oil dispersed in a flow-through system. After an exposure period of 8 to 21 d, elimination in organisms and devices was analyzed for 9 to 10 d following transfer to PAH-free seawater. Principal component analysis (PCA) revealed different PAH patterns. In mussel and SPMD, the PAH profiles were very close to that analyzed in seawater. Slight differences were, however, indicated for large molecules with log Kow above six. Nonachievement of steady-state concentration and bioavailability of PAH in oil droplets may account for these differences. The PAH composition in fish revealed only congeners with two to three aromatic rings. A combination of bioavailability and efficient metabolism of the larger PAH molecules may explain this pattern. The CFS made possible a better understanding of some critical factors governing bioconcentration in marine biota from dispersed oil. Yet the results illustrate that uptake of PAH from exposure to oil particles is complex and that different species may bioconcentrate different molecules depending on factors like life style and metabolic capability to degrade the potential harmful substances. Hence, risk assessment of the actual impact of discharges to marine biota should consider these essential biological and ecological factors.

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

[Concentrations and influencing factors of gaseous polycyclic aromatic hydrocarbons in residential air in Beijing].

PubMed

Wei, Zhi-cheng; Chang, Biao; Qiu, Wei-xun; Wang, Yi; Wu, Shi-min; Xing, Bao-shan; Liu, Wen-xin; Tao, Shu

2007-09-01

7 gas phase PAHs components in indoor air collected from 38 families were investigated by modified passive air samplers in Beijing areas during the local heating and non-heating seasons, and the influencing factors were discussed as well. The analytical results indicate that the gasous PAHs in local indoor air are dominated by 2 and 3 rings compounds, the mean concentrations for the 7 individual gaseous components range from 1 to 40 ng/m3, and the average concentration of total gaseous PAHs is about 100 ng/m3. There is no significant difference in total gaseous PAHs concentrations between the heating and the non-heating seasons, while some apparent seasonal changes occur in ACY and FLA concentrations. Compared with heating season, contribution of 2 rings compounds decreases while the proportions of 3 and 4 rings species increase during the non-heating season. Based on household activity questionnaires and actual analytical concentrations, the main influencing factors accounted for gaseous PAHs in indoor air, identified by multifactor analysis of variance, include cigarette smoking, use of moth ball, intensity of draft, cuisine frequency and built age.

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

Krasnokutski, Serge A., E-mail: skrasnokutskiy@yahoo.com; Huisken, Friedrich, E-mail: friedrich.huisken@uni-jena.de

The reaction of carbon atoms with benzene has been investigated in liquid helium droplets at T = 0.37 K. We found an addition of the carbon atom to form an initial intermediate complex followed by a ring opening and the formation of a seven-membered ring. In contrast to a previous gas phase study, the reaction is frozen after these steps and the loss of hydrogen does not occur. A calorimetric technique was applied to monitor the energy balance of the reaction. It was found that more than 267 kJ mol{sup −1} were released in this reaction. This estimation is inmore » line with quantum chemical calculations of the formation energy of a seven-membered carbon ring. It is suggested that reactions of this kind could be responsible for the low abundance of small polycyclic aromatic hydrocarbon molecules in the interstellar medium. We also found the formation of weakly bonded water-carbon adducts, in which the carbon atom is linked to the oxygen atom of the water molecule with a binding energy of about 33.4 kJ mol{sup −1}.« less

Centrohexaindane: six benzene rings mutually fixed in three dimensions - solid-state structure and six-fold nitration.

PubMed

Kuck, Dietmar; Linke, Jens; Teichmann, Lisa Christin; Barth, Dieter; Tellenbröker, Jörg; Gestmann, Detlef; Neumann, Beate; Stammler, Hans-Georg; Bögge, Hartmut

2016-04-28

The solid-state molecular structure of centrohexaindane (), a unique hydrocarbon comprising six benzene rings clamped to each other in three dimensions around a neopentane core, and the molecular packing in crystals of ·CHCl3 are reported. The molecular Td-symmetry and the Cartesian orientation of the six indane wings of in the solid state have been confirmed. The course and limitation of electrophilic aromatic substitution of are demonstrated for the case of nitration. Based on nitration experiments of a lower congener of , tribenzotriquinacene , the six-fold nitrofunctionalisation of has been achieved in excellent yield, giving four constitutional isomers, two nonsymmetrical ( and ) and two C3-symmetrical ones ( and ), all of which contain one single nitro group in each of the six benzene rings. The relative yields of the four isomers (∼3 : 1 : 1 : 3) point to a random electrophilic attack of the electrophiles at the twelve formally equivalent outer positions of the aromatic periphery of , suggesting electronic independence of its six aromatic π-electron systems. In turn, the pronounced conformational rigidity of the centrohexacyclic framework of enables the unequivocal structural identification of the isomeric hexanitrocentrohexaindanes by (1)H NMR spectroscopy.

DNA damage in marine rock oyster (Saccostrea Cucullata) exposed to environmentally available PAHs and heavy metals along the Arabian Sea coast.

PubMed

Sarker, Subhodeep; Vashistha, Deepti; Saha Sarker, Munmun; Sarkar, A

2018-04-30

Molecular biomarkers are used world wide for quick assessment of the immediate effect of environmental pollution on marine ecosystems. Recently, we evaluated oxidative stress responses of marine rock oyster, Saccostrea cucullata impacted due to polycyclic aromatic hydrocarbons (PAHs) accumulated in their tissues at a few sampling sites along the coast of Goa around the region of the Arabian sea coast, India (Sarkar et al., 2017). Using a combination of partial alkaline unwinding and comet assays, we now report a comprehensive study on the impairment of DNA integrity (DI) in S. cucullata due to exposure to environmentally available PAHs and also heavy metals (Pb, Cd, Cu, Fe and Mn) along the Arabian Sea coast, Goa, India exclusively around the entire coast of Goa. First, we determined significant correlation between DI in S. cucullata and the extent of exposure to and bioaccumulation of different PAH compounds including 2-3 aromatic ring PAHs (R 2 , 0.95), 4-6 aromatic ring PAHs (R 2 , 0.85), oxygenated-PAHs (oxy-PAHs, R 2 , 0.84) and total PAHs (t-PAHs, R 2 , 0.98). Second, we observed dose-dependent decrease in DI in S. cucullata with increasing concentrations of different PAH components in oyster tissues. We substantiated our field observations with appropriate laboratory controls using benzo[a]pyrene (BaP). Third, we performed stepwise multiple regression analyses of different water quality parameters including pH, salinity, temperature, dissolved oxygen (DO), biochemical oxygen demand (BOD), nitrite (NO 2 ), nitrate (NO 3 ), phosphate (PO 4 ), turbidity and also t-PAH-biota, t-PAH-water with DI as the dependent variable. Among all these parameters, only four parameters such as t-PAH-biota in combination with DO, BOD and NO 2 showed significant correlation (R¯ 2 = 0.95) with loss in DI in S. cucullata. Based on these results, we created a map indicating the percentage of DNA damage in S. cucullata exposed to PAHs and heavy metals at each sampling location along the west coast of India around Goa, India. Copyright © 2018 Elsevier Inc. All rights reserved.

Observational aspects of polycyclic aromatic hydrocarbon charging in the Interstellar Medium

NASA Technical Reports Server (NTRS)

Bakes, E. L. O.; Tielens, Alexander G. G. M.

1995-01-01

We have investigated the charging processes which affect small carbonaceous dust grains and polycyclic aromatic hydrocarbons (PAH's). Because of their high abundance, interstellar PAH molecules can dominate the charge balance of the interstellar medium (ISM), which controls the heating and cooling interstellar gas and interstellar chemistry. We present the results of our model, which compare well with observations and suggest further applications to both laboratory measurements and data obtainable from the KAO.

Water-Sediment Partition of Polycyclic Aromatic Hydrocarbons (PAHs) in Nansi Lake

NASA Astrophysics Data System (ADS)

Zhang, Guizhai; Diao, Youjiang

2018-06-01

Based on field data of polycyclic aromatic hydrocarbons (PAHs) in water and sediment in Nansi Lake. The concentrations and the partitioning characteristic of PAHs in the water and sediment were studied. The lgKd of high molecular weight PAHs were higher than the low molecular weight PAHs. The most of PAHs Kd values were negligible correlated with TOC, soluble salt, clay and pH of the sediment in Nansi Lake.

Monitoring of vapor phase polycyclic aromatic hydrocarbons

DOEpatents

Vo-Dinh, Tuan; Hajaligol, Mohammad R.

2004-06-01

An apparatus for monitoring vapor phase polycyclic aromatic hydrocarbons in a high-temperature environment has an excitation source producing electromagnetic radiation, an optical path having an optical probe optically communicating the electromagnetic radiation received at a proximal end to a distal end, a spectrometer or polychromator, a detector, and a positioner coupled to the first optical path. The positioner can slidably move the distal end of the optical probe to maintain the distal end position with respect to an area of a material undergoing combustion. The emitted wavelength can be directed to a detector in a single optical probe 180.degree. backscattered configuration, in a dual optical probe 180.degree. backscattered configuration or in a dual optical probe 90.degree. side scattered configuration. The apparatus can be used to monitor an emitted wavelength of energy from a polycyclic aromatic hydrocarbon as it fluoresces in a high temperature environment.

Direct photolysis of polycyclic aromatic hydrocarbons in drinking water sources.

PubMed

Sanches, S; Leitão, C; Penetra, A; Cardoso, V V; Ferreira, E; Benoliel, M J; Crespo, M T Barreto; Pereira, V J

2011-09-15

The widely used low pressure lamps were tested in terms of their efficiency to degrade polycyclic aromatic hydrocarbons listed as priority pollutants by the European Water Framework Directive and the U.S. Environmental Protection Agency, in water matrices with very different compositions (laboratory grade water, groundwater, and surface water). Using a UV fluence of 1500 mJ/cm(2), anthracene and benzo(a)pyrene were efficiently degraded, with much higher percent removals obtained when present in groundwater (83-93%) compared to surface water (36-48%). The removal percentages obtained for fluoranthene were lower and ranged from 13 to 54% in the different water matrices tested. Several parameters that influence the direct photolysis of polycyclic aromatic hydrocarbons were determined and their photolysis by-products were identified by mass spectrometry. The formation of photolysis by-products was found to be highly dependent on the source waters tested. Copyright © 2011 Elsevier B.V. All rights reserved.

Factors affecting elimination of polycyclic aromatic hydrocarbons from traditional smoked common carp meat

NASA Astrophysics Data System (ADS)

Babić, J.; Vidaković, S.; Škaljac, S.; Kartalović, B.; Ljubojević, D.; Ćirković, M.; Teodorović, V.

2017-09-01

Smoking techniques have been progressively improved and different procedures have been developed in different regions for treating fish. In these times, the technology is mainly used for enrichment of fish with specific taste and odour, to extend the shelf-life of these perishable products and appearance required widely on the market. A lot of chemical contaminants such as polycyclic aromatic hydrocarbons (PAHs) are formed during the combustion of fuel in the smoking process. PAHs are a group of compounds that have been the subject of great concern in the recent years due to their toxic, mutagenic and/or carcinogenic potentials to humans. These fact can have a significant impact on the acceptance of these products by consumers. In this review article, the objective is to describe factors affecting elimination of polycyclic aromatic hydrocarbons from traditional smoked common carp meat.

Absolute fragmentation cross sections in atom-molecule collisions: Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules

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

Chen, T.; Gatchell, M.; Stockett, M. H.

2014-06-14

We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH{sup +}) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH{sup +} + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C{sub 6}H{sub 5}). Thus nonstatistical fragmentation may be an effectivemore » initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.« less

Ingredients for Life (Artist's Concept)

NASA Technical Reports Server (NTRS)

2005-01-01

[figure removed for brevity, see original site] Figure 1: Artist's Conception Symbolically Represents Complex Organic Molecules

This artist's conception symbolically represents complex organic molecules, known as polycyclic aromatic hydrocarbons, seen in the early universe. These large molecules, comprised of carbon and hydrogen, are considered among the building blocks of life.

NASA's Spitzer Space Telescope is the first telescope to see polycyclic aromatic hydrocarbons so early -- 10 billion years further back in time than seen previously. Spitzer detected these molecules in galaxies when our universe was one-fourth of its current age of about 14 billion years.

These complex molecules are very common on Earth. They form any time carbon-based materials are not burned completely. They can be found in sooty exhaust from cars and airplanes, and in charcoal broiled hamburgers and burnt toast.

Polycyclic aromatic hydrocarbons are pervasive in galaxies like our own Milky Way, and play a significant role in star and planet formation.

Renal cancer risk and occupational exposure to polycyclic aromatic hydrocarbons and plastics

PubMed Central

Karami, Sara; Boffetta, Paolo; Brennan, Paul; Stewart, Patricia A.; Zaridze, David; Matveev, Vsevolod; Janout, Vladimir; Kollarova, Helena; Bencko, Vladimir; Navratilova, Marie; Szeszenia-Dabrowska, Neonila; Mates, Dana; Gromiec, Jan P.; Sobotka, Roman; Chow, Wong-Ho; Rothman, Nathaniel; Moore, Lee E.

2011-01-01

Objective To investigate whether occupational exposure to polycyclic aromatic hydrocarbons and certain plastic monomers increased renal cell carcinomas (RCC) risk. Methods Unconditional logistic regression was used to calculate RCC risk in relation to exposure. Results No association between RCC risk and having ever been occupationally exposed to any polycyclic aromatic hydrocarbons or plastics was observed. Duration of exposure and average exposure also showed no association with risk. Suggestive positive associations between RCC risk and cumulative exposure to styrene (P-trend = 0.02) and acrylonitrile (P-trend = 0.06) were found. Cumulative exposure to petroleum/gasoline engine emissions was inversely associated with risk (P-trend = 0.02). Conclusions Results indicate a possible association between occupational styrene and acrylonitrile exposure and RCC risk. Additional studies are needed to replicate findings, as this is the first time these associations have been reported and they may be due to chance. PMID:21270648

PRESSURE EFFECTS IN POLYCYCLIC AROMATIC NITROGENATED HETEROCYCLES (PANHs): DIAGNOSTIC QUALITIES AND COSMOBAROMETRY POTENTIAL

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

Montgomery, Wren; Sephton, Mark A., E-mail: w.montgomery@imperial.ac.uk

2016-03-01

The influence of polycyclic aromatic nitrogen heterocycles (PANHs), which have been suggested as contributors to the interstellar IR emission bands, on interstellar emission features is difficult to constrain because their infrared characteristics are strongly similar to those for polycyclic aromatic hydrocarbons (PAHs). One possible solution is to seek a means of visualizing the presence of PANHs that provides information that is distinct from that for PAHs. Although PANHs and PAHs have similar infrared characteristics in many settings, this relationship may not be universally maintained. We have used in situ high-pressure synchrotron-source Fourier transform infrared spectroscopy to determine that the responsesmore » of two representative molecules, acridine and anthracene, differ at high pressures (>ca. 1 GPa). Because there are a number of high-pressure environments that can be remotely observed by infrared spectroscopy, they represent a potential to glimpse the distribution of PANHs across the cosmos.« less

Four-dimensional data coupled to alternating weighted residue constraint quadrilinear decomposition model applied to environmental analysis: Determination of polycyclic aromatic hydrocarbons.

PubMed

Liu, Tingting; Zhang, Ling; Wang, Shutao; Cui, Yaoyao; Wang, Yutian; Liu, Lingfei; Yang, Zhe

2018-03-15

Qualitative and quantitative analysis of polycyclic aromatic hydrocarbons (PAHs) was carried out by three-dimensional fluorescence spectroscopy combining with Alternating Weighted Residue Constraint Quadrilinear Decomposition (AWRCQLD). The experimental subjects were acenaphthene (ANA) and naphthalene (NAP). Firstly, in order to solve the redundant information of the three-dimensional fluorescence spectral data, the wavelet transform was used to compress data in preprocessing. Then, the four-dimensional data was constructed by using the excitation-emission fluorescence spectra of different concentration PAHs. The sample data was obtained from three solvents that are methanol, ethanol and Ultra-pure water. The four-dimensional spectral data was analyzed by AWRCQLD, then the recovery rate of PAHs was obtained from the three solvents and compared respectively. On one hand, the results showed that PAHs can be measured more accurately by the high-order data, and the recovery rate was higher. On the other hand, the results presented that AWRCQLD can better reflect the superiority of four-dimensional algorithm than the second-order calibration and other third-order calibration algorithms. The recovery rate of ANA was 96.5%~103.3% and the root mean square error of prediction was 0.04μgL -1 . The recovery rate of NAP was 96.7%~115.7% and the root mean square error of prediction was 0.06μgL -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

On-road traffic emissions of polycyclic aromatic hydrocarbons and their oxy- and nitro- derivative compounds measured in road tunnel environments.

PubMed

Keyte, Ian J; Albinet, Alexandre; Harrison, Roy M

2016-10-01

Vehicular emissions are a key source of polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and their oxygenated (OPAH) and nitrated (NPAH) derivatives, in the urban environment. Road tunnels are a useful environment for the characterisation of on-road vehicular emissions, providing a realistic traffic fleet and a lack of direct sunlight, chemical reactivity and non-traffic sources. In the present investigation the concentrations of selected PAHs, OPAHs and NPAHs have been measured in the Parc des Princes Tunnel in Paris (PdPT, France), and at the Queensway Road Tunnel and an urban background site in Birmingham (QT, U.K). A higher proportion of semi-volatile (3-4 ring) PAH, OPAH and NPAH compounds are associated with the particulate phase compared with samples from the ambient environment. A large (~85%) decline in total PAH concentrations is observed between 1992 and 2012 measurements in QT. This is attributed primarily to the introduction of catalytic converters in the U.K as well as increasingly stringent EU vehicle emissions legislation. In contrast, NPAH concentrations measured in 2012 are similar to those measured in 1996. This observation, in addition to an increased proportion of (Phe+Flt+Pyr) in the observed PAH burden in the tunnel, is attributed to the increased number of diesel passenger vehicles in the U.K during this period. Except for OPAHs, comparable PAH and NPAH concentrations are observed in both investigated tunnels (QT and PdP). Significant differences are shown for specific substances between PAC chemical profiles in relation with the national traffic fleet differences (33% diesel passenger cars in U.K. vs 69% in France and up to 80% taking into account all vehicle categories). The dominating and sole contribution of 1-Nitropyrene observed in the PdPT NPAH profile strengthens the promising use of this compound as a diesel exhaust marker for PM source apportionment studies. Copyright © 2016 British Geological Survey, NERC. Published by Elsevier B.V. All rights reserved.

Seasonal changes of polycyclic aromatic hydrocarbons in response to hydrology and anthropogenic activities in the Pearl River estuary, China.

PubMed

Liu, Feng; Niu, Lixia; Chen, Hui; Li, Ping; Tian, Feng; Yang, Qingshu

2017-04-15

The behaviours of PAHs (containing 2-6 aromatic rings) in the Pearl River estuary were examined each month in 2011. This study was designed to investigate the abundance of 16 priority PAHs and their response to the seasonal dynamics of anthropogenic activities and hydrological cycles. Monthly mean concentrations of ∑ 16 PAHs in water and suspended particulate matter (SPM) were 88.31ng/L and 252.31ng/L respectively, with higher concentrations in the wet season (April to September). Heavy precipitation in the wet season resulted in relatively increased PAH input via riverine discharges and atmospheric deposition. Seasonal variations in suspended sediment concentration (SSC), temperature and salinity have considerably affected the PAH phase association. Higher SSC in the wet season contributed to higher concentration of the PAHs in SPM, and higher temperature and lower salinity facilitated desorption from SPM. The PAH sources were largely attributed to vehicular emissions, coal combustion and coke ovens. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

Brennan, Mathew D.; Spencer, Michelle J. S., E-mail: t-morishita@aist.go.jp, E-mail: michelle.spencer@rmit.edu.au; Morishita, Tetsuya, E-mail: t-morishita@aist.go.jp, E-mail: michelle.spencer@rmit.edu.au

Silicene is a relatively new material consisting of a two-dimensional sheet of silicon atoms. Functionalisation of silicene with different chemical groups has been suggested as a way to tune its electronic properties. In this work, density functional theory calculations and ab initio molecular dynamics simulations are used to examine the effects of functionalisation with naphthyl or anthracyl groups, which are two examples of small polycyclic aromatic hydrocarbons (PAHs). Different attachment positions on the naphthyl and anthracyl groups were compared, as well as different thicknesses of the silicene nanosheet. It was found that the carbon attachment position farthest from the bondmore » fusing the aromatic rings gave the more stable structures for both functional groups. All structures showed direct band gaps, with tuning of the band gap being achievable by increasing the length of the PAH or the thickness of the silicene. Hence, modifying the functional group or thickness of the silicene can both be used to alter the electronic properties of silicene making it a highly promising material for use in future electronic devices and sensors.« less

Source apportionment of PAH in Hamilton Harbour suspended sediments: comparison of two factor analysis methods.

PubMed

Sofowote, Uwayemi M; McCarry, Brian E; Marvin, Christopher H

2008-08-15

A total of 26 suspended sediment samples collected over a 5-year period in Hamilton Harbour, Ontario, Canada and surrounding creeks were analyzed for a suite of polycyclic aromatic hydrocarbons and sulfur heterocycles. Hamilton Harbour sediments contain relatively high levels of polycyclic aromatic compounds and heavy metals due to emissions from industrial and mobile sources. Two receptor modeling methods using factor analyses were compared to determine the profiles and relative contributions of pollution sources to the harbor; these methods are principal component analyses (PCA) with multiple linear regression analysis (MLR) and positive matrix factorization (PMF). Both methods identified four factors and gave excellent correlation coefficients between predicted and measured levels of 25 aromatic compounds; both methods predicted similar contributions from coal tar/coal combustion sources to the harbor (19 and 26%, respectively). One PCA factor was identified as contributions from vehicular emissions (61%); PMF was able to differentiate vehicular emissions into two factors, one attributed to gasoline emissions sources (28%) and the other to diesel emissions sources (24%). Overall, PMF afforded better source identification than PCA with MLR. This work constitutes one of the few examples of the application of PMF to the source apportionment of sediments; the addition of sulfur heterocycles to the analyte list greatly aided in the source identification process.

Characterization of selected volatile organic compounds, polycyclic aromatic hydrocarbons and carbonyl compounds at a roadside monitoring station

NASA Astrophysics Data System (ADS)

Ho, K. F.; Lee, S. C.; Chiu, Gloria M. Y.

Volatile organic compounds (VOCs), PAHs and carbonyl compounds are the major toxic components in Hong Kong. Emissions from motor vehicles have been one of the primary pollution sources in the metropolitan areas throughout Hong Kong for a long time. A 1-yr monitoring program for VOCs, PAHs and carbonyl compounds had been performed at a roadside urban station at Hong Kong Polytechnic University in order to determine the variations and correlations of each selected species (VOCs, PAHs and carbonyl compounds). This study is aimed to analyze toxic volatile organic compounds (benzene, toluene, ethylbenzene and xylene), two carbonyl compounds (formaldehyde, acetaldehyde), and selective polycyclic aromatic hydrocarbons. The monitoring program started from 16 April 1999 to 30 March 2000. Ambient VOC concentrations, many of which originate from the same sources as particulate PAHs and carbonyls compounds, show significant quantities of benzene, toluene and xylenes. Correlations and multivariate analysis of selected gaseous and particulate phase organic pollutants were performed. Source identification by principle component analysis and hierarchical cluster analysis allowed the identification of four sources (factors) for the roadside monitoring station. Factor 1 represents the effect of diesel vehicle exhaust. Factor 2 shows the contribution of aromatic compounds. Factor 3 explains photochemical products—formaldehyde and acetaldehyde. Factor 4 explains the effect of gasoline vehicle exhaust.

Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

PubMed

Hayen, Heiko; Michels, Antje; Franzke, Joachim

2009-12-15

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better.

Dynamic Response of Mycobacterium vanbaalenii PYR-1 to BP Deepwater Horizon Crude Oil

PubMed Central

Kim, Seong-Jae; Kweon, Ohgew; Sutherland, John B.; Kim, Hyun-Lee; Jones, Richard C.; Burback, Brian L.; Graves, Steven W.; Psurny, Edward

2015-01-01

We investigated the response of the hydrocarbon-degrading Mycobacterium vanbaalenii PYR-1 to crude oil from the BP Deepwater Horizon (DWH) spill, using substrate depletion, genomic, and proteome analyses. M. vanbaalenii PYR-1 cultures were incubated with BP DWH crude oil, and proteomes and degradation of alkanes and polycyclic aromatic hydrocarbons (PAHs) were analyzed at four time points over 30 days. Gas chromatography-mass spectrometry (GC-MS) analysis showed a chain length-dependent pattern of alkane degradation, with C12 and C13 being degraded at the highest rate, although alkanes up to C28 were degraded. Whereas phenanthrene and pyrene were completely degraded, a significantly smaller amount of fluoranthene was degraded. Proteome analysis identified 3,948 proteins, with 876 and 1,859 proteins up- and downregulated, respectively. We observed dynamic changes in protein expression during BP crude oil incubation, including transcriptional factors and transporters potentially involved in adaptation to crude oil. The proteome also provided a molecular basis for the metabolism of the aliphatic and aromatic hydrocarbon components in the BP DWH crude oil, which included upregulation of AlkB alkane hydroxylase and an expression pattern of PAH-metabolizing enzymes different from those in previous proteome expression studies of strain PYR-1 incubated with pure or mixed PAHs, particularly the ring-hydroxylating oxygenase (RHO) responsible for the initial oxidation of aromatic hydrocarbons. Based on these results, a comprehensive cellular response of M. vanbaalenii PYR-1 to BP crude oil was proposed. This study increases our fundamental understanding of the impact of crude oil on the cellular response of bacteria and provides data needed for development of practical bioremediation applications. PMID:25888169

Star-Shaped Conjugated Systems

PubMed Central

Detert, Heiner; Lehmann, Matthias; Meier, Herbert

2010-01-01

The present review deals with the preparation and the properties of star-shaped conjugated compounds. Three, four or six conjugated arms are attached to cross-conjugated cores, which consist of single atoms (B, C+, N), benzene or azine rings or polycyclic ring systems, as for example triphenylene or tristriazolotriazine. Many of these shape-persistent [n]star compounds tend to π-stacking and self-organization, and exhibit interesting properties in materials science: Linear and non-linear optics, electrical conductivity, electroluminescence, formation of liquid crystalline phases, etc.

Influence of silicon defects on the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons: a theoretical study using thiophene + coronene as the simplest model.

PubMed

Galano, Annia

2007-03-08

Physisorption and chemisorption processes of thiophene on coronene and 2Si-coronene have been studied using density functional theory and MP2 methods. These systems have been chosen as the simplest models to describe the adsorption of thiophene-like compounds on polycyclic aromatic hydrocarbons (PAHs). The calculated data suggest that the presence of silicon atoms in PAHs could favor their interaction with thiophene and similar compounds. Small stabilization energies have been found for several physisorbed complexes. The thiophene chemisorption on coronene seems very unlikely to occur, while that on 2Si-coronene leads to addition products which are very stable, with respect to the isolated reactants. These chemisorption processes were found to be exoergic (DeltaG < 0) in the gas phase and in the nonpolar liquid phase. The results reported in this work suggest that silicon defects on extended polycyclic aromatic hydrocarbons, such as graphite, soot, and large-diameter carbon nanotubes, could make them useful in the removal processes of aromatic sulfur compounds from oil hydrocarbons.

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.

Analyses at High Spatial Resolution of Organic Molecules in Extraterrestrial Samples: Two-Step Laser Mass Spectrometry: Search for Polycyclic Aromatic Hydrocarbons in Antarctic Meteorite and Micrometeorite Samples

NASA Technical Reports Server (NTRS)

Zare, Richard N.

1998-01-01

Perhaps the best way to summarize the past three-year grant period is to cite the publications and present a brief synopsis of each: 1. "Indigenous Polycyclic Aromatic Hydrocarbon Molecules in Circumstellar Graphite Grains." Bulk C-12/C-13 isotope ratios observed in some graphite grains extracted from primitive meteorites point strongly to a circumstellar origin. By applying our technique of microprobe two-step laser desorption laser ionization mass spectrometry ((mu)L(sup 2)MS) to individual circumstellar graphite grains we have measured the C-12/C-13 isotope ratio of various polycyclic aromatic hydrocarbons (PAHS) found in these grains. 2. "Deuterium Enrichments in Cluster IDPS," Large enrichments in the D/H isotope ratios in IDPs likely arise from the preservation of presolar molecules. 3. "Evidence for thermalization of surface-disorder molecules at heating rates of 10(exp 8) K/s". A careful study of the ((mu)L(sup 2)MS) of aniline-d(sub 7) from a single-crystal surface (0001) of sapphire (al2O3) shows that all measured properties are consistent with a thermal mechanism for desorption. 4. "Search for past life on Mars; possible relic biogenic activity in Martian meteorite ALH 84001. The authors examined the Martian meteorite ALH 84001 and found several lines of evidence compatible with existence of past primitive (single-cell) life on early Mars. 5. "Microprobe two-step laser mass spectrometry as an analytical tool for meteorite samples". THis paper presents a comprehensive review of (mu)L(sup 2)MS and how this technique can be applied to meteoritic samples. 6. "Indigenous polycyclic aromatic hydrocarbons in circumstellar graphite grains from primitive meteorites". The C-12/C-13 isotope ratios were measured for PAHs in a total of 89 spherical graphite grains. 7. "Observation of indigenous polycyclic aromatic hydrocarbons in "Giant" carbonaceous antarctic micrometeorites." The (mu)L(sup 2)MS method was used to establish the nature and distribution of PAHs in fragments of fifteen (approx. 200 microns) carbonaceous antarctic micrometeorites (AMMs). 8. "Evidence for the extraterrestrial origin of polycyclic aromatic hydrocarbons in the Martian meteorite ALH 84001" We have undertaken additional contamination studies of ALH 84001.

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.

Hollow Fiber Supported Ionic Liquids Liquid-Phase Micro-extraction Followed by High-Performance Liquid Chromatography for the Determination of Polycyclic Aromatic Hydrocarbons in Milk Samples.

PubMed

Wang, Meng; Cheng, Chunsheng; Liu, Chunbo; Yang, Yaling

2018-01-01

A rapid, simple, reliable and efficient hollow fiber supported ionic liquids liquid-phase micro-extraction method (IL-HF-LPME) followed by high-performance liquid chromatography was successfully applied to the determination of four kinds of polycyclic aromatic hydrocarbons (PAHs) in milk samples. In the IL-HF-LPME method, a mixture of [OMIM]PF6 and lauric acid, in a ratio of 3:1, was immobilized in the pores of a polypropylene hollow fiber used as extraction solvent. A series of essential parameters influencing the extraction efficiency were investigated and optimized. Under the optimal conditions, the extraction equilibrium is achieved within 3 min, the good linearity was >0.9990, the limits of detection varied from 0.14 to 0.71 ng/mL, the limit of quantification values were between 0.4 and 1.8 ng/mL, and the relative standard deviations were in the range of 1.24-3.27% (n = 5). The proposed method was applied to analyze four PAHs in milk samples and recoveries were between 93.6 and 102.8%. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Seasonal variations and sources of atmospheric polycyclic aromatic hydrocarbons and organochlorine compounds in a high-altitude city: Evidence from four-year observations

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

Gong, Ping; Wang, Xiaoping; Sheng, Jiujiang

Lijiang is a high-altitude city located on the eastern fringe of the Tibetan Plateau, with complex seasonal atmospheric circulations (i.e. westerly wind, Indian Monsoon, and East Asia Monsoon). Very few previous studies have focused on seasonal variations and sources of organic pollutants in Lijiang. In this study, a four-year air campaign from June 2009 to July 2013 was conducted to investigate the temporal trends and the sources of polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds [including organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs)]. The atmospheric PAH concentrations in winter are 2-3 times of those in summer, probably because of themore » combined result of enhanced local emission and long-range atmospheric transport (LRAT) during winter. Traffic pollution was the primary local source of PAHs, while biomass burning is the dominant LRAT source. Different from PAHs, OCPs and PCBs mainly underwent LRAT to reach Lijiang. The peak concentrations of most of OCPs occurred in pre-monsoon season and winter, which are carried by air masses from Myanmar and India through westerly winds. As compared with other sites of the Tibetan Plateau, without the direct barrier of the Himalaya, Lijiang is easily contaminated by the incursion of polluted air masses.« less

Seasonal variations and sources of atmospheric polycyclic aromatic hydrocarbons and organochlorine compounds in a high-altitude city: Evidence from four-year observations.

PubMed

Gong, Ping; Wang, Xiaoping; Sheng, Jiujiang; Wang, Hailong; Yuan, Xiaohua; He, Yuanqing; Qian, Yun; Yao, Tandong

2018-02-01

Lijiang is a high-altitude city located on the eastern fringe of the Tibetan Plateau, with complex seasonal atmospheric circulations (i.e. westerly wind, Indian Monsoon, and East Asia Monsoon). Very few previous studies have focused on seasonal variations and sources of organic pollutants in Lijiang. In this study, a four-year air campaign from June 2009 to July 2013 was conducted to investigate the temporal trends and the sources of polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds [including organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs)]. The atmospheric PAH concentrations in winter are 2-3 times of those in summer, probably because of the combined result of enhanced local emission and long-range atmospheric transport (LRAT) during winter. Traffic pollution was the primary local source of PAHs, while biomass burning is the dominant LRAT source. OCPs and PCBs also mainly underwent LRAT to reach Lijiang. The peak concentrations of most of OCPs occurred in pre-monsoon season and winter, which were carried by air masses from Myanmar and India through westerly winds. As compared with other sites of the Tibetan Plateau, without the direct barrier of the Himalaya, Lijiang is easily contaminated by the incursion of polluted air masses. Copyright © 2017 Elsevier Ltd. All rights reserved.

Seasonal effect and source apportionment of polycyclic aromatic hydrocarbons in PM2.5

NASA Astrophysics Data System (ADS)

Khan, Md Firoz; Latif, Mohd Talib; Lim, Chee Hou; Amil, Norhaniza; Jaafar, Shoffian Amin; Dominick, Doreena; Mohd Nadzir, Mohd Shahrul; Sahani, Mazrura; Tahir, Norhayati Mohd

2015-04-01

This study aims to investigate distribution and sources of 16 polycyclic aromatic hydrocarbons (PAHs) bound to fine particulate matter (PM2.5) captured in a semi-urban area in Malaysia during different seasons, and to assess their health risks. PM2.5 samples were collected using a high volume air sampler on quartz filter paper at a flow rate of 1 m3 min-1 for 24 h. PAHs on the filter paper were extracted with dichloromethane (DCM) using an ultrasonic centrifuge solid-phase extraction method and measured by gas chromatography-mass spectroscopy. The results showed that the range of PAHs concentrations in the study period was between 0.21 and 12.08 ng m-3. The concentrations of PAHs were higher during the south-west monsoon (0.21-12.08 ng m-3) compared to the north-east monsoon (0.68-3.80 ng m-3). The high molecular weight (HMW) PAHs (≥5 ring) are significantly prominent (>70%) compared to the low molecular weight (LMW) PAHs (≤4 ring) in PM2.5. The Spearman correlation indicates that the LMW and HMW PAHs correlate strongly among themselves. The diagnostic ratios (DRs) of I[c]P/I[c]P + BgP and B[a]P/B[g]P suggest that the HMW PAHs originated from fuel combustion sources. The source apportionment analysis of PAHs was resolved using DRs-positive matrix factorization (PMF)-multiple linear regression (MLR). The main sources identified were (a) gasoline combustion (65%), (b) diesel and heavy oil combustion (19%) and (c) natural gas and coal burning (15%). The health risk evaluation, by means of the lifetime lung cancer risk (LLCR), showed no potential carcinogenic risk from the airborne BaPeq (which represents total PAHs at the present study area in Malaysia). The seasonal LLCR showed that the carcinogenic risk of total PAHs were two fold higher during south-westerly monsoon compared to north-easterly monsoon.

Polycyclic aromatic hydrocarbons (PAHs) in indoor dust samples from Cities of Jeddah and Kuwait: Levels, sources and non-dietary human exposure.

PubMed

Ali, Nadeem; Ismail, Iqbal Mohammad Ibrahim; Khoder, Mamdouh; Shamy, Magdy; Alghamdi, Mansour; Costa, Max; Ali, Lulwa Naseer; Wang, Wei; Eqani, Syed Ali Musstjab Akber Shah

2016-12-15

This study reports levels and profiles of polycyclic aromatic hydrocarbons (PAHs) in dust samples collected from three different microenvironments (cars, air conditioner (AC) filters and household floor dust) of Jeddah, Saudi Arabia (KSA) and Kuwait. To the best of our knowledge, this is first study reporting PAHs in indoor microenvironments of KSA, which makes these findings important. Benzo(b)fluoranthene (BbF), benzo(a)pyrene (BaP), phenanthrene (Phe), and pyrene (Pyr) were found to be the major chemicals in dust samples from all selected microenvironments. ΣPAHs occurred at median concentrations (ng/g) of 3450, 2200, and 2650 in Saudi AC filter, car and household floor dust, respectively. The median levels (ng/g) of ΣPAHs in Kuwaiti car (950) and household floor (1675) dust samples were lower than Saudi dust. The PAHs profile in Saudi dust was dominated by high molecular weight (HMW) (4-5 ring) PAHs while in Kuwaiti dust 3 ring PAHs have marked contribution. BaP equivalent, a marker for carcinogenic PAHs, was high in Saudi household floor and AC filter dust with median levels (ng/g) of 370 and 455, respectively. Different exposure scenarios, using 5th percentile, median, mean, and 95th percentile levels, were estimated for adults and toddlers. For Saudi and Kuwaiti toddlers worst exposure scenario of ΣPAHs was calculated at 175 and 85ng/kg body weight/day (ng/kgbw/d), respectively. For Saudi toddlers, the calculated worst exposure scenarios for carcinogenic BaP (27.7) and BbF (29.3ng/kgbw/d) was 2-4 times higher than Kuwaiti toddlers. This study is based on small number of samples which necessitate more detailed studies for better understanding of dynamics of PAHs in the indoor environments of this region. Nevertheless, our finding supports the ongoing exposure of organic pollutants to population that accumulates indoor. Copyright © 2016. Published by Elsevier B.V.

Sources of polycyclic aromatic hydrocarbons in sediments of the Bharalu River, a tributary of the River Brahmaputra in Guwahati, India.

PubMed

Hussain, Karishma; Balachandran, S; Rafiqul Hoque, Raza

2015-12-01

Analysis of riverine sediments offers important information regarding anthropogenic activities in the adjacent watershed. In this study, we provide polycyclic aromatic hydrocarbon (PAH) levels, their possible sources and potential hazards in the Bharalu tributary of the Brahmaputra River flowing through Guwahati city in India. The USEPA's 16 priority PAHs were determined in river bank sediments during two distinct seasons viz. pre- and post-monsoon. The ∑PAHs concentrations varied between 338 and 23,100 ng g(-1) during post-monsoon and between 609 and 8620 ng g(-1) during pre-monsoon. Mean benzo(a)pyrene (BaP) levels were between 17.8 ± 12 and 21.9 ± 27 ng g(-1) during post- and pre-monsoon seasons respectively. Spatial variations were observed. Interestingly, bank sediment samples from the sites near the confluence of the Bharalu River with the Brahmaputra River were found to have maximum concentrations of PAHs during post-monsoon season. The profile of the PAHs was dominated by 3-, 4- and 6-ring compounds. We estimated hazards of PAHs as RQ∑PAHs, which showed seasonal variation: 3 times higher during post-monsoon than pre-monsoon. 3-and 4-ring PAHs were the major PAHs of concern. The Bharalu River sediment was found to pose medium to high hazards to ecosystem. The individual PAHs including Acy, Phen and Pyr were observed with RQ(MPCs) value >1 indicating severe hazards during post-monsoon and pre-monsoon season. A very high percentage of coefficient of variation (CV) for PAHs during post-monsoon also revealed great variation in hazards and sources in this season. The diagnostic ratios indicated both petrogenic and pyrogenic origin of the PAHs. The pyrogenic contributions were mainly attributed to emissions from diesel, gasoline and wood combustion which are mainly from anthropogenic sources. Copyright © 2015 Elsevier Inc. All rights reserved.

Concentrations and sources of polycyclic aromatic hydrocarbons in surface coastal sediments of the northern Gulf of Mexico

PubMed Central

2014-01-01

Background Coastal sediments in the northern Gulf of Mexico have a high potential of being contaminated by petroleum hydrocarbons, such as polycyclic aromatic hydrocarbons (PAHs), due to extensive petroleum exploration and transportation activities. In this study we evaluated the spatial distribution and contamination sources of PAHs, as well as the bioavailable fraction in the bulk PAH pool, in surface marsh and shelf sediments (top 5 cm) of the northern Gulf of Mexico. Results PAH concentrations in this region ranged from 100 to 856 ng g−1, with the highest concentrations in Mississippi River mouth sediments followed by marsh sediments and then the lowest concentrations in shelf sediments. The PAH concentrations correlated positively with atomic C/N ratios of sedimentary organic matter (OM), suggesting that terrestrial OM preferentially sorbs PAHs relative to marine OM. PAHs with 2 rings were more abundant than those with 5–6 rings in continental shelf sediments, while the opposite was found in marsh sediments. This distribution pattern suggests different contamination sources between shelf and marsh sediments. Based on diagnostic ratios of PAH isomers and principal component analysis, shelf sediment PAHs were petrogenic and those from marsh sediments were pyrogenic. The proportions of bioavailable PAHs in total PAHs were low, ranging from 0.02% to 0.06%, with higher fractions found in marsh than shelf sediments. Conclusion PAH distribution and composition differences between marsh and shelf sediments were influenced by grain size, contamination sources, and the types of organic matter associated with PAHs. Concentrations of PAHs in the study area were below effects low-range, suggesting a low risk to organisms and limited transfer of PAHs into food web. From the source analysis, PAHs in shelf sediments mainly originated from direct petroleum contamination, while those in marsh sediments were from combustion of fossil fuels. PMID:24641695

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.

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

PubMed

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

2018-08-15

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

Highly sensitive analysis of polycyclic aromatic hydrocarbons in environmental water with porous cellulose/zeolitic imidazolate framework-8 composite microspheres as a novel adsorbent coupled with high-performance liquid chromatography.

PubMed

Liang, Xiaotong; Liu, Shengquan; Zhu, Rong; Xiao, Lixia; Yao, Shouzhuo

2016-07-01

In this work, novel cellulose/zeolitic imidazolate frameworks-8 composite microspheres have been successfully fabricated and utilized as sorbent for environmental polycyclic aromatic hydrocarbons efficient extraction and sensitive analysis. The composite microspheres were synthesized through the in situ hydrothermal growth of zeolitic imidazolate frameworks-8 on cellulose matrix, and exhibited favorable hierarchical structure with chemical composition as assumed through scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction patterns, and Brunauer-Emmett-Teller surface areas characterization. A robust and highly efficient method was then successfully developed with as-prepared composite microspheres as novel solid-phase extraction sorbent with optimum extraction conditions, such as sorbent amount, sample volume, extraction time, desorption conditions, volume of organic modifier, and ionic strength. The method exhibited high sensitivity with low limit of detection down to 0.1-1.0 ng/L and satisfactory linearity with correlation coefficients ranging from 0.9988 to 0.9999, as well as good recoveries of 66.7-121.2% with relative standard deviations less than 10% for environmental polycyclic aromatic hydrocarbons analysis. Thus, our method was convenient and efficient for polycyclic aromatic hydrocarbons extraction and detection, potential for future environmental water samples analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2015-01-12

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

Emission characteristics of polycyclic aromatic hydrocarbons and nitro-polycyclic aromatic hydrocarbons from diesel trucks based on on-road measurements

NASA Astrophysics Data System (ADS)

Cao, Xinyue; Hao, Xuewei; Shen, Xianbao; Jiang, Xi; Wu, Bobo; Yao, Zhiliang

2017-01-01

Polycyclic aromatic hydrocarbon (PAH) and nitro-polycyclic aromatic hydrocarbon (NPAH) emissions from 18 diesel trucks of different sizes and with different emission standards were tested in Beijing using a portable emission measurement system (PEMS). Both the gaseous- and particulate-phase PAHs and NPAHs were quantified by high-performance liquid chromatography (HPLC) in the laboratory. The emission factors (EFs) of the total PAHs from light-duty diesel trucks (LDDTs), medium-duty diesel trucks (MDDTs) and heavy-duty diesel trucks (HDDTs) were 82229.11 ± 41906.06, 52867.43 ± 18946.47 and 93837.35 ± 32193.14 μg/km, respectively, much higher than the respective values of total NPAHs from their counterpart vehicles. The gaseous phase had an important contribution to the total PAHs and NPAHs, with a share rate of approximately 69% and 97% on average, respectively. The driving cycle had important impacts on the emissions of PAHs and NPAHs, especially for LDDTs and HDDTs. Higher emissions of PAHs and NPAHs were detected on non-highway roads compared to that on highways for these two types of vehicles. Compared to the results of different studies, the difference in the EFs of PAHs and NPAHs can reach several orders of magnitudes, which would introduce errors in the development of an emission inventory of PAHs and NPAHs.

Comparison of the solid-phase extraction efficiency of a bounded and an included cyclodextrin-silica microporous composite for polycyclic aromatic hydrocarbons determination in water samples.

PubMed

Mauri-Aucejo, Adela; Amorós, Pedro; Moragues, Alaina; Guillem, Carmen; Belenguer-Sapiña, Carolina

2016-08-15

Solid-phase extraction is one of the most important techniques for sample purification and concentration. A wide variety of solid phases have been used for sample preparation over time. In this work, the efficiency of a new kind of solid-phase extraction adsorbent, which is a microporous material made from modified cyclodextrin bounded to a silica network, is evaluated through an analytical method which combines solid-phase extraction with high-performance liquid chromatography to determine polycyclic aromatic hydrocarbons in water samples. Several parameters that affected the analytes recovery, such as the amount of solid phase, the nature and volume of the eluent or the sample volume and concentration influence have been evaluated. The experimental results indicate that the material possesses adsorption ability to the tested polycyclic aromatic hydrocarbons. Under the optimum conditions, the quantification limits of the method were in the range of 0.09-2.4μgL(-1) and fine linear correlations between peak height and concentration were found around 1.3-70μgL(-1). The method has good repeatability and reproducibility, with coefficients of variation under 8%. Due to the concentration results, this material may represent an alternative for trace analysis of polycyclic aromatic hydrocarbons in water trough solid-phase extraction. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced bioavailability of polyaromatic hydrocarbons in the form of mucin complexes.

PubMed

Drug, Eyal; Landesman-Milo, Dalit; Belgorodsky, Bogdan; Ermakov, Natalia; Frenkel-Pinter, Moran; Fadeev, Ludmila; Peer, Dan; Gozin, Michael

2011-03-21

Increasing exposure of biological systems to large amounts of polycyclic aromatic hydrocarbons is of great public concern. Organisms have an array of biological defense mechanisms, and it is believed that mucosal gel (which covers the respiratory system, the gastrointestinal tract, etc.) provides an effective chemical shield against a range of toxic materials. However, in this work, we demonstrate, for the first time, that, upon complexation of polyaromatic hydrocarbons with mucins, enhanced bioavailability and, therefore, toxicity are obtained. This work was aimed to demonstrate how complexation of various highly hydrophobic polycyclic aromatic hydrocarbons with representative mucin glycoprotein could lead to the formation of previously undescribed materials, which exhibit increased toxicity versus pristine polycyclic aromatic hydrocarbons. In the present work, we show that a representative mucin glycoprotein, bovine submaxillary mucin, has impressive and unprecedented capabilities of binding and solubilizing water-insoluble materials in physiological solution. The complexes formed between the mucin and a series of polycyclic aromatic hydrocarbons were comprehensively characterized, and their toxicity was evaluated by both in vivo and in vitro assays. In addition, the bioavailability and membrane-penetration capabilities were tested using an internalization assay. Our results provide, for the first time, evidence of an unknown route by which hydrophobic materials may achieve higher bioavailability, penetrating some of the biological defense systems, in the form of water-soluble complexes with mucosal proteins.

Nuclear Magnetic Resonance Studies of an N2-Guanine Adduct Derived from the Tumorigen Dibenzo[a,l]pyrene in DNA: Impact of Adduct Stereochemistry, Size, and Local DNA Sequence on Solution Conformations

PubMed Central

2015-01-01

The dimensions and arrangements of aromatic rings (topology) in adducts derived from the reactions of polycyclic aromatic hydrocarbon (PAH) diol epoxide metabolites with DNA influence the distortions and stabilities of double-stranded DNA, and hence their recognition and processing by the human nucleotide excision repair (NER) system. Dibenzo[a,l]pyrene (DB[a,l]P) is a highly tumorigenic six-ring PAH, which contains a nonplanar and aromatic fjord region that is absent in the structurally related bay region five-ring PAH benzo[a]pyrene (B[a]P). The PAH diol epoxide–DNA adducts formed include the stereoisomeric 14S and 14Rtrans-anti-DB[a,l]P-N2-dG and the stereochemically analogous 10S- and 10R-B[a]P-N2-dG (B[a]P-dG) guanine adducts. However, nuclear magnetic resonance (NMR) solution studies of the 14S-DB[a,l]P-N2-dG adduct in DNA have not yet been presented. Here we have investigated the 14S-DB[a,l]P-N2-dG adduct in two different sequence contexts using NMR methods with distance-restrained molecular dynamics simulations. In duplexes with dC opposite the adduct deleted, a well-resolved base-displaced intercalative adduct conformation can be observed. In full duplexes, in contrast to the intercalated 14R stereoisomeric adduct, the bulky DB[a,l]P residue in the 14S adduct is positioned in a greatly widened and distorted minor groove, with significant disruptions and distortions of base pairing at the lesion site and two 5′-side adjacent base pairs. These unique structural features are significantly different from those of the stereochemically analogous but smaller B[a]P-dG adduct. The greater size and different topology of the DB[a,l]P aromatic ring system lead to greater structurally destabilizing DNA distortions that are partially compensated by stabilizing DB[a,l]P-DNA van der Waals interactions, whose combined effects impact the NER response to the adduct. These structural results broaden our understanding of the structure–function relationship in NER. PMID:24617538

Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames.

PubMed

Ruwe, Lena; Moshammer, Kai; Hansen, Nils; Kohse-Höinghaus, Katharina

2018-04-25

In this study, we experimentally investigate the high-temperature oxidation kinetics of n-pentane, 1-pentene and 2-methyl-2-butene (2M2B) in a combustion environment using flame-sampling molecular beam mass spectrometry. The selected C5 fuels are prototypes for linear and branched, saturated and unsaturated fuel components, featuring different C-C and C-H bond structures. It is shown that the formation tendency of species, such as polycyclic aromatic hydrocarbons (PAHs), yielded through mass growth reactions increases drastically in the sequence n-pentane < 1-pentene < 2M2B. This comparative study enables valuable insights into fuel-dependent reaction sequences of the gas-phase combustion mechanism that provide explanations for the observed difference in the PAH formation tendency. First, we investigate the fuel-structure-dependent formation of small hydrocarbon species that are yielded as intermediate species during the fuel decomposition, because these species are at the origin of the subsequent mass growth reaction pathways. Second, we review typical PAH formation reactions inspecting repetitive growth sequences in dependence of the molecular fuel structure. Third, we discuss how differences in the intermediate species pool influence the formation reactions of key aromatic ring species that are important for the PAH growth process underlying soot formation. As a main result it was found that for the fuels featuring a C[double bond, length as m-dash]C double bond, the chemistry of their allylic fuel radicals and their decomposition products strongly influences the combination reactions to the initially formed aromatic ring species and as a consequence, the PAH formation tendency.

Magnetic nanoparticles-nylon 6 composite for the dispersive micro solid phase extraction of selected polycyclic aromatic hydrocarbons from water samples.

PubMed

Reyes-Gallardo, Emilia M; Lucena, R; Cárdenas, S; Valcárcel, M

2014-06-06

In this article, the easy synthesis of magnetic nanoparticles-nylon 6 composite is presented, characterized and applied in the microextraction field. The one-step synthesis of the composite is performed by a solvent changeover playing with the different solubility of the polymeric network in formic acid and water. The new material has been characterized by different techniques including infrared spectroscopy, transmission and scanning microscopy. The extraction performance of the composite under a dispersive micro solid phase extraction format has been evaluated by determining four polycyclic aromatic hydrocarbons (benzo[b]fluoranthene, fluoranthene, indeno[1,2,3-cd]pyrene and phenanthrene) in water using ultra performance liquid chromatography (UPLC) combined with photo diode array detection. The developed methodology allows the determination of the analytes with limits of detection in the range from 0.05 μg/L (benzo[b]fluoranthene) to 0.58 μg/L (phenanthrene). The repeatability of the method was better than 6.9% at the limit of quantification level. The relative recoveries varied in the interval 80-111%. Copyright © 2014 Elsevier B.V. All rights reserved.

Polycyclic aromatic hydrocarbons - fate and long-range atmospheric transport studied using a global model, EMAC-SVOC

NASA Astrophysics Data System (ADS)

Octaviani, Mega; Tost, Holger; Lammel, Gerhard

2017-04-01

Polycyclic aromatic hydrocarbons (PAHs) are emitted by incomplete combustion from fossil fuel, vehicles, and biomass burning. They may persist in environmental compartments, pose a health hazard and may bio accumulate along food chains. The ECHAM/MESSy Atmospheric Chemistry (EMAC) model had been used to simulate global tropospheric, stratospheric chemistry and climate. In this study, we improve the model to include simulations of the transport and fate of semi-volatile organic compounds (SVOC). The EMAC-SVOC model takes into account essential environmental processes including gas-particle partitioning, dry and wet deposition, chemical and bio-degradation, and volatilization from sea surface, soils, vegetation, and snow. The model was evaluated against observational data in the Arctic, mid-latitudes, and tropics, and further applied to study total environmental lifetime and long-range transport potential (LRTP) of PAHs. We selected four compounds for study, spanning a wide range of volatility, i.e., phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene. Several LRTP indicators were investigated, including the Arctic contamination potential, meridional spreading, and zonal and meridional fluxes to remote regions.