Use of constant wavelength synchronous spectrofluorimetry for identification of polycyclic aromatic hydrocarbons in air particulate samples

NASA Astrophysics Data System (ADS)

Sharma, Homdutt; Jain, V. K.; Khan, Zahid H.

2013-05-01

We have developed a simple, rapid, inexpensive method for the identification of fluoranthene (Flan), benz(a)anthracene (BaA), benzo(a)pyrene (BaP), benzo(k)fluoranthene (BkF), pyrene (Pyr), benz(ghi)perylene (BghiP) in suspended particulate matter in an urban environment of Delhi. Suspended particulate matter samples of 24 h duration were collected on glass fiber filter papers. Polycyclic aromatic hydrocarbons (PAHs) were extracted from the filter papers using dichloromethane (DCM) and hexane with ultrasonication method. Comparison of the characteristic emission of spectra of PAHs with standard spectra indicated the degree of condensation of aromatic compounds present in investigated mixtures. It was also possible to identify some individual compounds. However, this identification could be more effective with the use of the respective values of Δλ parameter for each particular component of the mixture.

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

PubMed

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

2012-12-01

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

Metabolism of 7-nitrogenz[a]anthracene by intestinal microflora

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

Morehead, M.C.; Franklin, W.; Fu, P.P.

1994-12-31

Pure cultures of anaerobic intestinal bacteria and mixed fecal microflora from human, rat, mouse, and pig were screened for the ability to metabolize 7-nitrobenz[a]anthracene. Based on analysis by high-performance liquid chromatography (HPLC) and by ultraviolent (UV), mass, and nuclear magnetic resonance (NMR) spectral techniques, the compounds were identified as 7-aminobenz[a]anthracene and benz[a]anthracene 7,12-dione. Identification of 7-NH{sub 2}BA as a metabolite of 7-NO{sub 2}BA indicates that the anaerobic intestinal bacteria are capable of reducing 7-NO{sub 2}BA to potentially bioactive intermediates. The reductive capacities of the mixed intestinal microflora were generally greater than those of pure cultures. Thus, metabolism of 7-NO{sub 2}BAmore » in the intestinal tract may be underestimated if pure cultures are used as the sole method for evaluating the potential hazard.« less

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

Removal of Two High Molecular Weight PAHs from Soils with Different Water Content.

PubMed

Corona, Lilia; Dendooven, Luc; Chicken, Anaí; Hernández, Omar; Iturbe, Rosario

2017-11-01

Polycyclic aromatic hydrocarbons (PAHs) such as benz[a]anthracene (BA) and dibenz[a,h]anthracene (DBA), which are considered toxic, are frequently found in contaminated soils in Mexico. A laboratory-scale study monitored the degradation of the mixture of these two PAHs in three soils from different Mexican states (Tabasco, Morelos and Veracruz), each with different organic matter content, particle size distribution and incubated under different water content conditions. The hydrocarbons were extracted using microwave digestion and quantified by GC/MS. The removal of the PAHs, the growth of aerobic bacteria and microbial activity were determined in soil samples with and without a bacterial growth inhibitor (HgCl 2 ). The conclusion is that more than 90% of both contaminants was removed from the three soils, independently of the soil water content or the application of a bacterial growth inhibitor. Biological properties of the soils showed changes at the end of the experiment, but the results of the removal of PAHs were similar in the three soils.

Draft genome sequence of marine Streptomyces sp. strain W007, which produces angucyclinone antibiotics with a benz[a]anthracene skeleton.

PubMed

Qin, Song; Zhang, Hongyu; Li, Fuchao; Zhu, Benwei; Zheng, Huajun

2012-03-01

A series of angucyclinone antibiotics have been isolated from marine Streptomyces sp. strain W007 and identified. Here, a draft genome sequence of Streptomyces sp. W007 is presented. The genome contains an intact biosynthetic gene cluster for angucyclinone antibiotics, which provides insight into the combinatorial biosynthesis of angucyclinone antibiotics produced by marine streptomycetes.

Tumor initiating activities of various derivatives of benz(a)anthracene and 7, 12-dimethyl-benz(a)anthracene in mouse skin

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

Slaga, T.J.; Gleason, G.L.; DiGiovanni, J.

Current information indicates that polycyclic aromatic hydrocarbons (PAH) exert their toxic, mutagenic, and carcinogenic activities after they have been metabolically activated by target cells to reactive epoxides. The results obtained from IN VIVO and IN VITRO binding, mutagenicity, metabolism, and carcinogenicity studies have led to the conclusion that BP-7, 8-diol is a proximate carcinogenic metabolite of BP, and the BP-diol-epoxide is an ultimate carcinogenic metabolite of BP. Recent results concerning the strong carcinogenicity of BP-7..beta.., 8..cap alpha..-diol-9..cap alpha..,10..cap alpha..-epoxide in newborn mice and in mouse skin strongly indicate that it is the ultimate carcinogenic metabolite of BP. Since diol-epoxides maymore » be responsible for the carcinogenicity of PAH other than BP, diols and diol-epoxides as well as other derivatives of PAH were tested for skin tumor-initiation in a two-stage system of tumorigenesis. In addition, since activation of methylated PAH may involve the side-chain methyl group, the skin tumor-initiating activity of various side-chain derivatives of methylated PA were determined. In this report, the skin tumor initiation of various derivatives of a nonmethylated PAH, BA as well as a methylated PAH, DMBA are compared. The data suggest that bay region diol-epoxides may be important in BA and DMBA carcinogenicity in mice which is supportive of the theory proposed by Jerina and co-workers which predicts that diol-epoxides in the bay region are the major determinants of PAH carcinogenicity.« less

Polycyclic aromatic hydrocarbons in commercial fish and lobsters from the coastal waters of Madagascar following an oil spill in August 2009.

PubMed

Rumney, Heather S; Laruelle, Franck; Potter, Kerry; Mellor, Philip K; Law, Robin J

2011-12-01

Concentrations of polycyclic aromatic hydrocarbons were determined in species of commercial fish and lobsters following an oil-spill just off the protected Madagascan coastline. Samples were collected along the coastline within and outside the affected area. Summed PAH concentrations ranged from 1.9 μg kg(-1) to 63 μg kg(-1) wet weight, but with no higher molecular weight PAHs (>202 Da) being detected. All concentrations of benzo[a]pyrene, benz[a]anthracene and dibenz[a,h]anthracene were <0.1 μg kg(-1) wet weight, well within the EU and UK set limits for the protection of human health. Additionally, samples were calculated as the benzo[a]pyrene toxic equivalency quotient (TEQ) and found to be well below the level of concern in relation to health of human consumers. Evaluation of the biota PAH data indicated the origin of PAH was predominantly petrogenic with >80% arising from oil sources. Profile studies indicate a low-level multisource petrogenic contamination probably representing a pre-spill background for the area. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

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.

Comparative analysis of the electrostatic potentials of some structural analogues of 2,3,7,8-tetrachlorodibenzo-p-dioxin and of related aromatic systems

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

Murray, J.S.; Evans, P.; Politzer, P.

1990-01-01

An ab initio STO-5G computational analysis of the electrostatic potentials of four structural analogs of the highly toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and four related aromatic systems (benzo(a)pyrene, benz(a)anthracene and two isomeric benzoflavones) was carried out. The systems, to varying degrees, induce aryl hydrocarbon hydroxylase activity and are believed to interact with the same cytosolic receptor in initiating their biochemical responses. It was found that a high degree of activity appears to require negative potentials that are non-overlapping above all or most of the lateral regions, with an observed optimum range of magnitudes. In systems with central oxygens, it is required thatmore » the negative oxygen potentials be small and weak; however, oxygen negative regions in the molecule are not necessary for high activity. The observed differences between the potential patterns of the four aromatic systems and those of TCDD and its active analogs may reflect an inherent dissimilarity in the nature of their interactions with the cytosolic receptor.« less

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

PubMed Central

Zelinkova, Zuzana; Wenzl, Thomas

2015-01-01

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

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

PubMed

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

2007-04-01

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

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

PubMed Central

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

2012-01-01

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

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.

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

PubMed

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

2017-03-22

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

Effect of mangrove black tea extract from Ceriops decandra (Griff.) on hematology and biochemical changes in dimethyl benz[a]anthracene-induced hamster buccal pouch carcinogenesis.

PubMed

Sithranga Boopathy, N; Kathiresan, K; Jeon, Y J

2011-09-01

Effect of the black tea extracted from a mangrove plant species, Ceriops decandra (Griff.) was studied on dimethyl benz[a]anthracene (DMBA)-induced changes in blood hematology and plasma non-enzymatic antioxidants in male hamsters. Hamsters were painted with 0.5% solution of DMBA in liquid paraffin on the right buccal pouch three times in a week up to 14 weeks. Each application treated with 0.4mg of DMBA. The mangrove black tea extract (MBTE) was administrated orally with 5mgkg(-1) twice a day and then with DMBA on alternate days. Results showed that the DMBA caused a significant (P<0.05) decline in the levels of reduced glutathione (GSH), vitamin-C, -E, red blood cells, hemoglobin, mean corpuscular volume and hematocrit; and increase in the levels of WBC, platelets, lymphocytes and neutrophils. The MBTE prevented the DMBA-induced adverse changes significantly in blood and biochemical parameters of the male hamsters. This work concluded that the black tea extracted from the coastal mangrove species C. decandra prevented the DMBA-induced buccal pouch carcinogenesis in hamsters. Copyright © 2011 Elsevier B.V. All rights reserved.

Nuclear factor kappa B: a pro-inflammatory, transcription factor-mediated signalling pathway in lung carcinogenesis and its inhibition by nonsteroidal anti-inflammatory drugs.

PubMed

Setia, Shruti; Sanyal, Sankar Nath

2012-01-01

9,10-Dimethyl benz(a)anthracene (DMBA), when injected intratracheally once at a dose of 20 mg/kg body weight, is found to induce lung cancer in rats. Two nonsteroidal anti-inflammatory drugs (NSAIDs), indomethacin and etoricoxib, are given orally daily as chemopreventive agents at a dose of 0.6 mg/kg body weight and 2 mg/kg body weight, respectively, along with DMBA. Morphologic and histologic analysis revealed the occurence of tumors and intense cellular proliferation in the DMBA-treated animals, whereas no such features were observed in the other groups. Nuclear factor κB, a nuclear transcription factor, and proliferating cell nuclear antigen, a cell proliferation antigen, were studied by immunoblotting and immunohistochemistry and their levels were markedly elevated in the DMBA group compared with the others. Oxidative stress parameters, as studied by the inducible nitric oxide synthase activity, and the levels of reactive oxygen and nitrogen species were found to be suppressed in the DMBA group. Furthermore, fluorescent staining of the isolated lung cells from bronchoalveolar lavage was performed to study apoptosis and alterations in the mitochondrial membrane potential, and the DMBA-induced lung cancer was found to be associated with high inner mitochondrial membrane potential and a suppressed level of apoptosis.

Combined ultrasound with Fenton treatment for the degradation of carcinogenic polycyclic aromatic hydrocarbons in textile dying sludge.

PubMed

Zhang, Jian-Hao; Zou, Hai-Yuan; Ning, Xun-An; Lin, Mei-Qing; Chen, Chang-Min; An, Tai-Cheng; Sun, Jian

2017-03-22

To develop an effective method to remove the toxic and carcinogenic polycyclic aromatic hydrocarbons (CPAHs) from textile dyeing sludge, five CPAHs were selected to investigate the degradation efficiencies using ultrasound combined with Fenton process (US/Fenton). The results showed that the synergistic effect of the US/Fenton process on the degradation of CPAHs in textile dyeing sludge was significant with the synergy degree of 30.4. During the US/Fenton process, low ultrasonic density showed significant advantage in degrading the CPAHs in textile dyeing sludge. Key reaction parameters on CPAHs degradation were optimized by the central composite design as followed: H 2 O 2 concentration of 152 mmol/L, ultrasonic density of 408 W/L, pH value of 3.7, the molar ratio of H 2 O 2 to Fe 2+ of 1.3 and reaction time of 43 min. Under the optimal conditions of the US/Fenton process, the degradation efficiencies of five CPAHs were obtained as 81.23% (benzo[a]pyrene) to 84.98% (benz[a]anthracene), and the benzo[a]pyrene equivalent (BaP eq ) concentrations of five CPAHs declined by 81.22-85.19%, which indicated the high potency of US/Fenton process for removing toxic CPAHs from textile dyeing sludge.

Effects of red mold dioscorea on oral carcinogenesis in DMBA-induced hamster animal model.

PubMed

Hsu, Wei-Hsuan; Lee, Bao-Hong; Pan, Tzu-Ming

2011-06-01

Monascus-fermented products offer valuable therapeutic benefits and have been extensively used for centuries in East Asia. Dioscorea has been proved to have anti-cancer effect. The aim of this study is to investigate the anti-tumor ability of the ethanol extract of red mold dioscorea (RMDE) on 7,12-dimethyl-1,2-benz[a]anthracene (DMBA)-induced hamster buccal pouch carcinogenesis. We induced oral squamous cell carcinoma (OSCC) in the buccal pouch of male Syrian golden hamsters by painting with 0.5% DMBA three times a week for 14 weeks. From 9 to 14 weeks, a dose of 50, 100, and 200 mg RMDE per kg body weight were painting with the hamsters for 6 weeks on days alternate to the DMBA application. The results demonstrated that RMDE decreased nitric oxide (NO), reactive oxygen species (ROS), and prostaglandin E(2) (PGE(2)) overexpression in hamster buccal pouches in the DMBA treatment group and increased p53, serum tumor necrosis factor-α (TNF-α), and interleukin-1β (IL-1β) to significantly stimulate caspase-8 and -3 activities, indicating that RMDE reduced oxidative damage causing by DMBA and induced apoptosis in oral cancer cells. Therefore, RMDE may have therapeutic potentials against OSCC. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

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

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

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

Chemopreventive effects of NSAIDs as inhibitors of cyclooxygenase-2 and inducers of apoptosis in experimental lung carcinogenesis.

PubMed

Setia, Shruti; Vaish, Vivek; Sanyal, Sankar Nath

2012-07-01

Roles of cyclooxygenase (COX) enzyme and intrinsic pathway of apoptosis have been explored for the chemopreventive effects of non-steroidal anti-inflammatory drugs (NSAIDs) on 9,10-dimethyl benz(a)anthracene (DMBA)-induced lung cancer in rat model. 16 weeks after the administration of DMBA, morphological analysis revealed the occurrences of tumours and lesions, which were regressed considerably with the co-administration of indomethacin and etoricoxib, the two NSAIDs under investigation. DMBA group was marked by hyperplasia and dysplasia as observed by histological examination, and these features were corrected to a large extent by the two NSAIDs. Elevated levels of COX-2 were seen in the DMBA group, the enzyme responsible for prostaglandin synthesis during inflammation and cancer, whilst the expression of the constitutive isoform, COX-1, was equally expressed in all the groups. Apoptosis was quantified by studying the activities of apaf-1, caspase-9, and 3 by immunofluorescence and western blots. Their activities were found to diminish in the DMBA-treated animals as compared to the other groups. Fluorescent co-staining of the isolated broncho-alveolar lavage cells showed reduced number of apoptotic cells in the DMBA group, indicating decrease in apoptosis after carcinogen administration. The present results thus suggest that the mechanism of cancer chemoprevention of NSAIDs may include the suppression of COX-2 and the induction of apoptosis.

Raman spectroscopic investigation of the chemopreventive response of naringenin and its nanoparticles in DMBA-induced oral carcinogenesis

NASA Astrophysics Data System (ADS)

Krishnakumar, N.; Sulfikkarali, N. K.; Manoharan, S.; Venkatachalam, P.

2013-11-01

Raman spectroscopy is a vibrational spectroscopic technique that can be used to optically probe the biomolecular changes associated with tumor progression. The aim of the present study is to investigate the biomolecular changes in chemopreventive response of prepared naringenin-loaded nanoparticles (NARNPs) relative to efficacy of free naringenin (NAR) during 7,12-dimethyl benz(a)anthracene (DMBA)-induced oral carcinogenesis by Fourier Transform Raman (FT-Raman) spectroscopy. Oral squamous cell carcinoma (OSCC) was developed in the buccal pouch of golden Syrian hamsters by painting with 0.5% DMBA in liquid paraffin three times a week for 14 weeks. Raman spectra differed significantly between the control and tumor tissues, with tumors showing higher percentage signals for nucleic acids, phenylalanine and tryptophan and a lower in the percentage of phospholipids. Moreover, oral administration of free NAR and NARNPs significantly increased phospholipids and decreased the levels of tryptophan, phenylalanine and nucleic acid contents. On a comparative basis, NARNPs was found to have a more potent antitumor effect than free NAR in completely preventing the formation of squamous cell carcinoma and in improving the biochemical status to a normal range in DMBA-induced oral carcinogenesis. The present study further suggest that Raman spectroscopy could be a valuable tool for rapid and sensitive detection of specific biomolecular changes in response to chemopreventive agents.

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

Chemoprevention of skin cancer by the flavonoid fraction of Saraca asoka.

PubMed

Cibin, T R; Devi, D Gayathri; Abraham, Annie

2010-05-01

Saraca asoka (Family - Caesalpiniaceae) has been widely used in the Ayurvedic (traditional Indian) system of medicine especially due to its wound healing property. The present study investigated the chemopreventive property of flavonoids from the flowers of Saraca asoka on 7,12 dimethyl benz(a)anthracene (DMBA) induced skin cancer in mice models. A single topical application of DMBA (100 microg/50 microL of acetone) followed after 2 weeks by three times a week treatment with croton oil (1% in acetone), for 20 weeks resulted in tumor induction. The topical application of the flavonoid fraction of S. asoka (FF S. asoka), 30 min prior to the application of croton oil thrice weekly for 20 weeks, caused a significant reduction in the number of tumors per mouse and the percentage of tumor-bearing mice. Also the latency period for the appearance of the first tumor was delayed by S. asoka pretreatment. In the flavonoid fraction (5 mg and 10 mg/kg body weight) treated animals, the levels of biochemical markers - rhodanese, myeloperoxidase, beta-D-glucuronidase, sialic acid, hexokinase and caspase 3 were significantly restored to near normal levels. These findings suggest the chemopreventive activity of flavonoids from S. asoka on two stage skin carcinogenesis. Histological data also support the chemopreventive potential of S. asoka. Copyright (c) 2009 John Wiley & Sons, Ltd.

Proposal for a screening test to evaluate the fate of organic micropollutants in activated sludge.

PubMed

Salvetti, Roberta; Vismara, Renato; Dal Ben, Ilaria; Gorla, Elena; Romele, Laura

2011-04-01

The concentrations of organic micropollutants are usually low in wastewaters (order of magnitude of mg L(-1)). However, their emission standards, especially in the case of carcinogenic and bioaccumulating substances, are often much lower (order of magnitude of microg L(-1)). Since these substances, in some cases, can be adsorbable or volatile, their removal via volatilization, biodegradation or sludge adsorption in a wastewater treatment plant (WWTP) becomes a significant feature to include in the usual design process, in order to verify the emission standards in gas and sludge too. In this study a simple screening batch test for the evaluation of the fate of organic micropollutants in water, air and sludge is presented. The test is set up by means of simple laboratory instruments and simulates an activated sludge tank process. In this study the results obtained for four substances with different chemical properties (i.e. toluene, benz(a)anthracene, phenol and benzene) are presented. The screening test proposed can be a useful tool to assess in about one month the fate of organic micropollutants in an activated sludge tank of a WWTP. Moreover, the test can constitute a useful support in the use of mathematical models, since it allows the verification of model results and the calibration of the reactions involved in the removal process.

Changes in PAH levels during production of rapeseed oil.

PubMed

Cejpek, K; Hajslová, J; Kocourek, V; Tomaniová, M; Cmolík, J

1998-07-01

The influence of technological operations during rapeseed oil production on polycyclic aromatic hydrocarbon (PAH) concentrations in by-products, intermediate and final oils was evaluated. The decrease of light PAHs, benz(a)anthracene and benzo(a)pyrene during processing of crude oil to the deodorized product was significant at the 95% confidence interval in most batches analysed. Deodorization and alkali-refining were the steps contributing most to the PAH decrease. The relationship between PAH levels in rapeseed (and consequently in refined oil) and the duration of storage period was studied. The contamination of raw material processed a short time after harvesting was significantly higher than that of the rapeseed stored in silos for several months. Analyses of rapeseed samples, which were re-purified in the laboratory, revealed that solid particles, which contaminate rapeseed during harvesting, initial treatment, transport and storage, contributed to PAH contamination to the extent of 36% (light PAHs) to 64% (heavy PAHs) on average. Further experiments demonstrated that PAHs in re-purified rapeseed were concentrated in the cuticular layer, because they were removed well from the whole seeds by simple rinsing with organic solvent in an ultrasonic bath without losses of rapeseed oil. Alternative expressions of total PAH contamination (e.g. various PAH groups and/or differently defined B(a)P toxic equivalents) are discussed and their effect on drawing conclusions about PAH elimination rate has been demonstrated.

Monohydroxylated polycyclic aromatic hydrocarbons influence spicule formation in the early development of sea urchins (Hemicentrotus pulcherrimus).

PubMed

Suzuki, Nobuo; Ogiso, Shouzo; Yachiguchi, Koji; Kawabe, Kimi; Makino, Fumiya; Toriba, Akira; Kiyomoto, Masato; Sekiguchi, Toshio; Tabuchi, Yoshiaki; Kondo, Takashi; Kitamura, Kei-ichiro; Hong, Chun-Sang; Srivastav, Ajai K; Oshima, Yuji; Hattori, Atsuhiko; Hayakawa, Kazuichi

2015-05-01

We previously demonstrated that monohydroxylated polycyclic aromatic hydrocarbons (OHPAHs), which are metabolites of polycyclic aromatic hydrocarbons (PAHs), act on calcified tissue and suppress osteoblastic and osteoclastic activity in the scales of teleost fish. The compounds may possibly influence other calcified tissues. Thus, the present study noted the calcified spicules in sea urchins and examined the effect of both PAHs and OHPAHs on spicule formation during the embryogenesis of sea urchins. After fertilization, benz[a]anthracene (BaA) and 4-hydroxybenz[a]anthracene (4-OHBaA) were added to seawater at concentrations of 10(-8) and 10(-7) M and kept at 18 °C. The influence of the compound was given at the time of the pluteus larva. At this stage, the length of the spicule was significantly suppressed by 4-OHBaA (10(-8) and 10(-7) M). BaA (10(-7) M) decreased the length of the spicule significantly, while the length did not change with BaA (10(-8) M). The expression of mRNAs (spicule matrix protein and transcription factors) in the 4-OHBaA (10(-7) M)-treated embryos was more strongly inhibited than were those in the BaA (10(-7) M)-treated embryos. This is the first study to demonstrate that OHPAHs suppress spicule formation in sea urchins. Copyright © 2015 Elsevier Inc. All rights reserved.

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

USGS Publications Warehouse

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

2001-01-01

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

Contamination of Tea and Tea Infusion with Polycyclic Aromatic Hydrocarbons

PubMed Central

Zachara, Alicja; Gałkowska, Dorota; Juszczak, Lesław

2017-01-01

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

Assessment of pollution of the Boca de Camichin Estuary in Nayarit (Mexico) and its influence on oxidative stress in Crassostrea corteziensis oysters.

PubMed

Toledo-Ibarra, G A; Díaz Resendiz, K J G; Ventura-Ramón, G H; Romero-Bañuelos, C A; Medina-Díaz, I M; Rojas-García, A E; Vega-López, A; Girón-Pérez, M I

2016-10-01

Boca de Camichin Estuary is one of the main producers of Crassostrea corteziensis oysters in Mexico, but the presence of pollutants can affect oyster production. Molluscs produce reactive oxygen species (ROS) in response to changes in the environment and pollution. These ROS induce oxidative damage in biomolecules. The main objective of this study was to evaluate pollution in the estuary and the subsequent oxidative stress in C. corteziensis oysters during the 2010 production cycle. For this aim, we performed monthly samplings in the oyster farms from January to May. We took water samples to quantify polycyclic aromatic hydrocarbon (PAH) and metal content; also, we evaluated oxidative damage (lipoperoxidation, lipidic hydroperoxides, protein oxidation) and enzyme activity (CAT, SOD, GPx, GST and AChE) in oyster gills. The results show the presence of Cu, Fe, Mn, naphthalene, benz[a]anthracene, pyrene, benz[a]pyrene and benzo[k]fluoranthene. On the other hand, AChE activity was not inhibited, which suggests that organophosphorus pollutants or carbamates were absent. Regarding oxidative stress, oysters from the estuary had oxidative damage in lipids, not proteins, and altered antioxidant enzyme activity, when compared to control organisms. Interestingly, we did not observe any correlation between the pollutants and the oxidative stress parameters evaluated in this study. Thus, we cannot rule out that a synergistic effect between the environmental variables and the pollutants is causing the oxidative stress in these oysters. Copyright © 2016 Elsevier Inc. All rights reserved.

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

PubMed

Szaniszló, J; Ungváry, G

2001-03-09

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

APPI-MS: Effects of mobile phases and VUV lamps on the detection of PAH compounds

PubMed Central

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A.

2009-01-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of non-polar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e., ≤100 μL/min), while at a higher flow, photon absorption and ion-molecule reactions become significant. Under certain circumstances, APPI signal and S/N have been observed to excel at higher flow, which may be due to a non-photoionzation mechanism. To better understand APPI at higher flow rates, we have selected three lamps (Xe, Kr and Ar) and four mobile phases typical for reverse-phase, high-pressure liquid chromatography: acetonitrile, methanol, (1:1) acetonitrile:water and (1:1) methanol:water. As test compounds, three polyaromatic hydrocarbons are studied: benzo[a]pyrene, indeno[1,2,3-c,d]pyrene and benz[a]anthracene. We find that solvent photoabsorption cross-section is not the only parameter in explaining relative signal intensity, but that solvent photo-ion chemistry can also play a significant role. Three conclusions from this investigation are: (i) Methanol photoionization leads to protonated methanol clusters that can result in chemical ionization of analyte molecule; (ii) Use of the Ar lamp often results in greater signal and S/N; (iii) Acetonitrile photoionization is less efficient and resulting clusters are too strongly bound to efficiently chemically ionize the analyte, so that analyte ion formation is dominated by direct photoionization. PMID:17188507

PAH determination based on a rapid and novel gas purge-microsyringe extraction (GP-MSE) technique in road dust of Shanghai, China: Characterization, source apportionment, and health risk assessment.

PubMed

Zheng, Xin; Yang, Yi; Liu, Min; Yu, Yingpeng; Zhou, John L; Li, Donghao

2016-07-01

A novel cleanup technique termed as gas purge-microsyringe extraction (GP-MSE) was evaluated and applied for polycyclic aromatic hydrocarbon (PAH) determination in road dust samples. A total of 68 road dust samples covering almost the entire Shanghai area were analyzed for 16 priority PAHs using gas chromatography-mass spectrometry. The results indicate that the total PAH concentrations over the investigated sites ranged from 1.04μg/g to 134.02μg/g dw with an average of 13.84μg/g. High-molecular-weight compounds (4-6 rings PAHs) were significantly dominant in the total mass of PAHs, and accounted for 77.85% to 93.62%. Diagnostic ratio analysis showed that the road dust PAHs were mainly from the mixture of petroleum and biomass/coal combustions. Principal component analysis in conjunction with multiple linear regression indicated that the two major origins of road dust PAHs were vehicular emissions and biomass/fossil fuel combustions, which contributed 66.7% and 18.8% to the total road dust PAH burden, respectively. The concentration of benzo[a]pyrene equivalent (BaPeq) varied from 0.16μg/g to 24.47μg/g. The six highly carcinogenic PAH species (benz(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, dibenz(a,h)anthracene, and indeno(1,2,3-cd)pyrene) accounted for 98.57% of the total BaPeq concentration. Thus, the toxicity of PAHs in road dust was highly associated with high-molecular-weight compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Ligand-Specific Transcriptional Mechanisms Underlie Aryl Hydrocarbon Receptor-Mediated Developmental Toxicity of Oxygenated PAHs

PubMed Central

Goodale, B. C.; La Du, J.; Tilton, S. C.; Sullivan, C. M.; Bisson, W. H.; Waters, K. M.; Tanguay, R. L.

2015-01-01

Polycyclic aromatic hydrocarbons (PAHs) are priority environmental contaminants that exhibit mutagenic, carcinogenic, proinflammatory, and teratogenic properties. Oxygen-substituted PAHs (OPAHs) are formed during combustion processes and via phototoxidation and biological degradation of parent (unsubstituted) PAHs. Despite their prevalence both in contaminated industrial sites and in urban air, OPAH mechanisms of action in biological systems are relatively understudied. Like parent PAHs, OPAHs exert structure-dependent mutagenic activities and activation of the aryl hydrocarbon receptor (AHR) and cytochrome p450 metabolic pathway. Four-ring OPAHs 1,9-benz-10-anthrone (BEZO) and benz(a)anthracene-7,12-dione (7,12-B[a]AQ) cause morphological aberrations and induce markers of oxidative stress in developing zebrafish with similar potency, but only 7,12-B[a]AQ induces robust Cyp1a protein expression. We investigated the role of the AHR in mediating the toxicity of BEZO and 7,12-B[a]AQ, and found that knockdown of AHR2 rescued developmental effects caused by both compounds. Using RNA-seq and molecular docking, we identified transcriptional responses that precede developmental toxicity induced via differential interaction with AHR2. Redox-homeostasis genes were affected similarly by these OPAHs, while 7,12-B[a]AQ preferentially activated phase 1 metabolism and BEZO uniquely decreased visual system genes. Analysis of biological functions and upstream regulators suggests that BEZO is a weak AHR agonist, but interacts with other transcriptional regulators to cause developmental toxicity in an AHR-dependent manner. Identifying ligand-dependent AHR interactions and signaling pathways is essential for understanding toxicity of this class of environmentally relevant compounds. PMID:26141390

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

PubMed

Akdoğan, Abdullah; Buttinger, Gerhard; Wenzl, Thomas

2016-01-01

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

APPI-MS: effects of mobile phases and VUV lamps on the detection of PAH compounds.

PubMed

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A

2007-04-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of nonpolar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e., benz[a]anthracene. We find that solvent photoabsorption cross-section is not the only parameter in explaining relative signal intensity, but that solvent photo-ion chemistry can also play a significant role. Three conclusions from this investigation are: (1) methanol photoionization leads to protonated methanol clusters that can result in chemical ionization of analyte molecule; (2) use of the Ar lamp often results in greater signal and S/N; (3) acetonitrile photoionization is less efficient and resulting clusters are too strongly bound to chemically ionize the analyte efficiently, so that analyte ion formation is dominated by direct photoionization.

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

NASA Astrophysics Data System (ADS)

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

2015-11-01

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

Aquatic predicted no-effect concentrations of 16 polycyclic aromatic hydrocarbons and their ecological risks in surface seawater of Liaodong Bay, China.

PubMed

Wang, Ying; Wang, Juying; Mu, Jingli; Wang, Zhen; Cong, Yi; Yao, Ziwei; Lin, Zhongsheng

2016-06-01

Polycyclic aromatic hydrocarbons (PAHs), a class of ubiquitous pollutants in marine environments, exhibit moderate to high adverse effects on aquatic organisms and humans. However, the lack of PAH toxicity data for aquatic organism has limited evaluation of their ecological risks. In the present study, aquatic predicted no-effect concentrations (PNECs) of 16 priority PAHs were derived based on species sensitivity distribution models, and their probabilistic ecological risks in seawater of Liaodong Bay, Bohai Sea, China, were assessed. A quantitative structure-activity relationship method was adopted to achieve the predicted chronic toxicity data for the PNEC derivation. Good agreement for aquatic PNECs of 8 PAHs based on predicted and experimental chronic toxicity data was observed (R(2)  = 0.746), and the calculated PNECs ranged from 0.011 µg/L to 205.3 µg/L. A significant log-linear relationship also existed between the octanol-water partition coefficient and PNECs derived from experimental toxicity data (R(2)  = 0.757). A similar order of ecological risks for the 16 PAH species in seawater of Liaodong Bay was found by probabilistic risk quotient and joint probability curve methods. The individual high ecological risk of benzo[a]pyrene, benzo[b]fluoranthene, and benz[a]anthracene needs to be determined. The combined ecological risk of PAHs in seawater of Liaodong Bay calculated by the joint probability curve method was 13.9%, indicating a high risk as a result of co-exposure to PAHs. Environ Toxicol Chem 2016;35:1587-1593. © 2015 SETAC. © 2015 SETAC.

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

PubMed

Chen, Edward S; Chen, Edward C M

2018-02-15

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

Ligand-specific transcriptional mechanisms underlie aryl hydrocarbon receptor-mediated developmental toxicity of oxygenated PAHs

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

Goodale, B. C.; Geisel School of Medicine at Dartmouth, Hanover, NH; La Du, J.

Polycyclic aromatic hydrocarbons (PAHs) are priority environmental contaminants that exhibit mutagenic, carcinogenic, proinflammatory, and teratogenic properties. Oxygen-substituted PAHs (OPAHs) are formed during combustion processes and via phototoxidation and biological degradation of parent (unsubstituted) PAHs. Despite their prevalence both in contaminated industrial sites and in urban air, OPAH mechanisms of action in biological systems are relatively understudied. Like parent PAHs, OPAHs exert structure-dependent mutagenic activities and activation of the aryl hydrocarbon receptor (AHR) and cytochrome p450 metabolic pathway. Four-ring OPAHs 1,9-benz-10-anthrone (BEZO) and benz(a)anthracene-7,12-dione (7,12-B[a]AQ) cause morphological aberrations and induce markers of oxidative stress in developing zebrafish with similar potency, butmore » only 7,12-B[a]AQ induces robust Cyp1a protein expression. We investigated the role of the AHR in mediating the toxicity of BEZO and 7,12-B[a]AQ, and found that knockdown of AHR2 rescued developmental effects caused by both compounds. Using RNA-seq and molecular docking, we identified transcriptional responses that precede developmental toxicity induced via differential interaction with AHR2. Redox-homeostasis genes were affected similarly by these OPAHs, while 7,12-B[a]AQ preferentially activated phase 1 metabolism and BEZO uniquely decreased visual system genes. Analysis of biological functions and upstream regulators suggests that BEZO is a weak AHR agonist, but interacts with other transcriptional regulators to cause developmental toxicity in an AHR-dependent manner. Furthermore, identifying ligand-dependent AHR interactions and signaling pathways is essential for understanding toxicity of this class of environmentally relevant compounds.« less

Ligand-specific transcriptional mechanisms underlie aryl hydrocarbon receptor-mediated developmental toxicity of oxygenated PAHs

DOE PAGES

Goodale, B. C.; Geisel School of Medicine at Dartmouth, Hanover, NH; La Du, J.; ...

2015-07-03

Polycyclic aromatic hydrocarbons (PAHs) are priority environmental contaminants that exhibit mutagenic, carcinogenic, proinflammatory, and teratogenic properties. Oxygen-substituted PAHs (OPAHs) are formed during combustion processes and via phototoxidation and biological degradation of parent (unsubstituted) PAHs. Despite their prevalence both in contaminated industrial sites and in urban air, OPAH mechanisms of action in biological systems are relatively understudied. Like parent PAHs, OPAHs exert structure-dependent mutagenic activities and activation of the aryl hydrocarbon receptor (AHR) and cytochrome p450 metabolic pathway. Four-ring OPAHs 1,9-benz-10-anthrone (BEZO) and benz(a)anthracene-7,12-dione (7,12-B[a]AQ) cause morphological aberrations and induce markers of oxidative stress in developing zebrafish with similar potency, butmore » only 7,12-B[a]AQ induces robust Cyp1a protein expression. We investigated the role of the AHR in mediating the toxicity of BEZO and 7,12-B[a]AQ, and found that knockdown of AHR2 rescued developmental effects caused by both compounds. Using RNA-seq and molecular docking, we identified transcriptional responses that precede developmental toxicity induced via differential interaction with AHR2. Redox-homeostasis genes were affected similarly by these OPAHs, while 7,12-B[a]AQ preferentially activated phase 1 metabolism and BEZO uniquely decreased visual system genes. Analysis of biological functions and upstream regulators suggests that BEZO is a weak AHR agonist, but interacts with other transcriptional regulators to cause developmental toxicity in an AHR-dependent manner. Furthermore, identifying ligand-dependent AHR interactions and signaling pathways is essential for understanding toxicity of this class of environmentally relevant compounds.« less

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

PubMed

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

2017-11-01

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

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

PubMed Central

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

2009-01-01

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

Effect of chemical mutagens and carcinogens on gene expression profiles in human TK6 cells.

PubMed

Godderis, Lode; Thomas, Reuben; Hubbard, Alan E; Tabish, Ali M; Hoet, Peter; Zhang, Luoping; Smith, Martyn T; Veulemans, Hendrik; McHale, Cliona M

2012-01-01

Characterization of toxicogenomic signatures of carcinogen exposure holds significant promise for mechanistic and predictive toxicology. In vitro transcriptomic studies allow the comparison of the response to chemicals with diverse mode of actions under controlled experimental conditions. We conducted an in vitro study in TK6 cells to characterize gene expression signatures of exposure to 15 genotoxic carcinogens frequently used in European industries. We also examined the dose-responsive changes in gene expression, and perturbation of biochemical pathways in response to these carcinogens. TK6 cells were exposed at 3 dose levels for 24 h with and without S9 human metabolic mix. Since S9 had an impact on gene expression (885 genes), we analyzed the gene expression data from cells cultures incubated with S9 and without S9 independently. The ribosome pathway was affected by all chemical-dose combinations. However in general, no similar gene expression was observed among carcinogens. Further, pathways, i.e. cell cycle, DNA repair mechanisms, RNA degradation, that were common within sets of chemical-dose combination were suggested by clustergram. Linear trends in dose-response of gene expression were observed for Trichloroethylene, Benz[a]anthracene, Epichlorohydrin, Benzene, and Hydroquinone. The significantly altered genes were involved in the regulation of (anti-) apoptosis, maintenance of cell survival, tumor necrosis factor-related pathways and immune response, in agreement with several other studies. Similarly in S9+ cultures, Benz[a]pyrene, Styrene and Trichloroethylene each modified over 1000 genes at high concentrations. Our findings expand our understanding of the transcriptomic response to genotoxic carcinogens, revealing the alteration of diverse sets of genes and pathways involved in cellular homeostasis and cell cycle control.

Effect of Chemical Mutagens and Carcinogens on Gene Expression Profiles in Human TK6 Cells

PubMed Central

Godderis, Lode; Thomas, Reuben; Hubbard, Alan E.; Tabish, Ali M.; Hoet, Peter; Zhang, Luoping; Smith, Martyn T.; Veulemans, Hendrik; McHale, Cliona M.

2012-01-01

Characterization of toxicogenomic signatures of carcinogen exposure holds significant promise for mechanistic and predictive toxicology. In vitro transcriptomic studies allow the comparison of the response to chemicals with diverse mode of actions under controlled experimental conditions. We conducted an in vitro study in TK6 cells to characterize gene expression signatures of exposure to 15 genotoxic carcinogens frequently used in European industries. We also examined the dose-responsive changes in gene expression, and perturbation of biochemical pathways in response to these carcinogens. TK6 cells were exposed at 3 dose levels for 24 h with and without S9 human metabolic mix. Since S9 had an impact on gene expression (885 genes), we analyzed the gene expression data from cells cultures incubated with S9 and without S9 independently. The ribosome pathway was affected by all chemical-dose combinations. However in general, no similar gene expression was observed among carcinogens. Further, pathways, i.e. cell cycle, DNA repair mechanisms, RNA degradation, that were common within sets of chemical-dose combination were suggested by clustergram. Linear trends in dose–response of gene expression were observed for Trichloroethylene, Benz[a]anthracene, Epichlorohydrin, Benzene, and Hydroquinone. The significantly altered genes were involved in the regulation of (anti-) apoptosis, maintenance of cell survival, tumor necrosis factor-related pathways and immune response, in agreement with several other studies. Similarly in S9+ cultures, Benz[a]pyrene, Styrene and Trichloroethylene each modified over 1000 genes at high concentrations. Our findings expand our understanding of the transcriptomic response to genotoxic carcinogens, revealing the alteration of diverse sets of genes and pathways involved in cellular homeostasis and cell cycle control. PMID:22723965

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

PubMed

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

2017-04-01

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

Elimination of deleterious effects of DMBA-induced skin carcinogenesis in mice by Syzygium cumini seed extract.

PubMed

Parmar, Jyoti; Sharma, Priyanka; Verma, Preeti; Sharma, Priyanka; Goyal, Pradeep K

2011-09-01

The inhibition of tumor incidence by hydro-alcoholic extract of S.cumini seed was evaluated in mice on two stage process of skin carcinogenesis induced by single application of 7, 12-dimethyl benz(a)anthracene (100 µg/100µl of acetone), and 2 weeks later promoted by repeated application of croton oil (1% acetone/thrice in a week) till the end of the experiment (i.e. 16 weeks). Oral administration of extract at a dose of 250mg/kg b.wt./day at the peri-initiational stage (i.e. 7 days before and 7 days after DMBA application), promotional stage (i.e. from the time of croton oil application) and at both the stages (i.e. 7 days prior to DMBA application & continued till the end of experiment) to the mice, recorded a significant reduction in tumor incidence to 37.5, 50 & 25% respectively in comparison to the carcinogen treated control, where tumor incidence was found as 100%. Tumor yield and Tumor burden were also significantly reduced by SCE. Similarly, the cumulative number of papillomas after 16 weeks was 68 in the control group, which was reduced to 15, 21 & 8 in the animals treated with the SCE continuously at peri-, post- and peri- & post- initiation stage respectively. A significant impairment was noticed in the levels of reduced glutathione, superoxide dismutase, catalase & protein and enhancement in LPO in liver and skin of carcinogen treated control mice as compared with vehicle treated mice. All such parameters were returned to near normal value by administration of SCE to DMBA treated mice. These results suggest a possible chemopreventive property of S.cumini against DMBA induced skin carcinogenesis in mice.

Metabolism of the tropine indole-3-carboxylate ICS 205-930 by differentiated rat and human hepatoma cells.

PubMed

Fischer, V; Baldeck, J P; Wiebel, F J

The metabolism of the tropine indole-3-carboxylate ICS 205-930 (ICS), a highly potent and selective antagonist of 5-HT3 receptors, was investigated in continuous cell lines derived from rat or human liver and compared to the in vivo metabolism in rat and human. The well-differentiated rat hepatoma line 2sFou extensively metabolized ICS by hydroxylation of the indole moiety and subsequent conjugation to form the corresponding glucuronides and sulfates. The 2sFou cells also oxidized ICS at the tropinyl moiety to form both N-demethyl and N-oxide derivatives. The relative amount of the various metabolites was dependent on the substrate concentration. Pretreatment of the cells with dexamethasone increased the rate of metabolism for all pathways, while benz[a]anthracene caused an increase in hydroxylation at the indole moiety at the expense of N-oxidation. Phenobarbital pretreatment had no effect on ICS metabolism. The pattern of metabolites formed in 2sFou cells was qualitatively similar to that formed in rat urine. The human hepatoma line HepG2 metabolized ICS only to a small extent. The HepG2 cells failed to form detectable amounts of ICS conjugates found in human urine. The N-oxide-ICS was not found in HepG2 cells or in human urine. Virtually no ICS metabolites were found in human lung adenocarcinoma lines NCI-H358 or NCI-H322. The results suggest that continuous cell lines such as the differentiated rat hepatoma cells 2sFou might be used to mimic the metabolism of xenobiotics in rat and to clarify their complex metabolic pathways.

Polycyclic aromatic hydrocarbons (PAHs) in the settled dust of automobile workshops, health and carcinogenic risk evaluation.

PubMed

Ali, Nadeem; Ismail, Iqbal Mohammad Ibrahim; Khoder, Mamdouh; Shamy, Magdy; Alghamdi, Mansour; Al Khalaf, Abdulrahman; Costa, Max

2017-12-01

There are studies available on the occurrence of PAHs in indoor settled dust from residential and different occupational settings in literature but limited data is available on their occurrence and potential health risk assessment in automobile workshops. In recent decades Saudi Arabia has experienced tremendous growth in the petroleum industry and as a result, the automobile industry is booming. People working in automobile workshops are at a greater risk of exposure to chemicals releasing from the petroleum products. The main objective of this study was to report PAHs in settled dust from different automobile workshops of Jeddah, Saudi Arabia, and evaluate health risk for workers through dust exposure. Pyrene (1585-13500ng/g), Benz[a]anthracene (

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

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

PubMed

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

2016-09-01

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

Celecoxib prevents colitis associated colon carcinogenesis: an upregulation of apoptosis.

PubMed

Setia, Shruti; Nehru, Bimla; Sanyal, Sankar N

2014-12-01

Uncontrolled cell proliferation and suppressed apoptosis are the critical events transforming a normal cell to a cancerous one wherein the inflammatory microenvironment supports this oncogenic transformation. The process of colon carcinogenesis may be aggravated in chronic inflammatory conditions such as ulcerative colitis where non-steroidal anti-inflammatory drugs (NSAIDs) may effectively prevent the cellular and molecular events. Western blots and immunofluorescent analysis of DNA mismatch repair enzymes, cell cycle regulators and pro- and anti-apoptotic proteins were performed in dextran sulfate sodium (DSS)-induced ulcerative colitis and 1,2-dimethyl benz(a)anthracene (DMH)-induced colon cancer. Also, apoptotic studies were done in isolated colonocytes using fluorescent staining and in paraffin sections using TUNEL assay. An upregulation of cell cycle regulators: cyclin D1/cdk4 and cyclin E/cdk2 and anti-apoptotic Bcl-2, along with the suppression of DNA repair enzymes: MLH1 and MSH2; tumour suppressors: p53, p21and Rb and pro-apoptotic proteins: Bax and Bad were observed in the DSS, DMH and DSS+DMH groups. Proliferating cell nuclear antigen (PCNA) was also overexpressed in these groups. The ultimate executioner of the apoptotic pathway; caspase-3, was suppressed in these groups. Apoptotic studies in colonocytes and paraffin sections revealed suppressed apoptosis in these groups. These effects were corrected with the administration of a second generation NSAID, celecoxib along with the treatment of DSS and DMH. The chemopreventive action of celecoxib in colitis mediated colon carcinogenesis may include the regulation of DNA mismatch repair enzymes, cell cycle check points, cell proliferation and apoptosis. Copyright © 2014 Institute of Pharmacology, Polish Academy of Sciences. Published by Elsevier Urban & Partner Sp. z o.o. All rights reserved.

Ligand-Specific Transcriptional Mechanisms Underlie Aryl Hydrocarbon Receptor-Mediated Developmental Toxicity of Oxygenated PAHs.

PubMed

Goodale, B C; La Du, J; Tilton, S C; Sullivan, C M; Bisson, W H; Waters, K M; Tanguay, R L

2015-10-01

Polycyclic aromatic hydrocarbons (PAHs) are priority environmental contaminants that exhibit mutagenic, carcinogenic, proinflammatory, and teratogenic properties. Oxygen-substituted PAHs (OPAHs) are formed during combustion processes and via phototoxidation and biological degradation of parent (unsubstituted) PAHs. Despite their prevalence both in contaminated industrial sites and in urban air, OPAH mechanisms of action in biological systems are relatively understudied. Like parent PAHs, OPAHs exert structure-dependent mutagenic activities and activation of the aryl hydrocarbon receptor (AHR) and cytochrome p450 metabolic pathway. Four-ring OPAHs 1,9-benz-10-anthrone (BEZO) and benz(a)anthracene-7,12-dione (7,12-B[a]AQ) cause morphological aberrations and induce markers of oxidative stress in developing zebrafish with similar potency, but only 7,12-B[a]AQ induces robust Cyp1a protein expression. We investigated the role of the AHR in mediating the toxicity of BEZO and 7,12-B[a]AQ, and found that knockdown of AHR2 rescued developmental effects caused by both compounds. Using RNA-seq and molecular docking, we identified transcriptional responses that precede developmental toxicity induced via differential interaction with AHR2. Redox-homeostasis genes were affected similarly by these OPAHs, while 7,12-B[a]AQ preferentially activated phase 1 metabolism and BEZO uniquely decreased visual system genes. Analysis of biological functions and upstream regulators suggests that BEZO is a weak AHR agonist, but interacts with other transcriptional regulators to cause developmental toxicity in an AHR-dependent manner. Identifying ligand-dependent AHR interactions and signaling pathways is essential for understanding toxicity of this class of environmentally relevant compounds. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Structurally distinct polycyclic aromatic hydrocarbons induce differential transcriptional responses in developing zebrafish

PubMed Central

Goodale, Britton C.; Tilton, Susan C.; Wilson, Glenn; Corvi, Margaret M.; Janszen, Derek B.; Anderson, Kim A.; Waters, Katrina M.; Tanguay, Robert L.

2014-01-01

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment as components of fossil fuels and by-products of combustion. These multi-ring chemicals differentially activate the Aryl Hydrocarbon Receptor (AHR) in a structurally dependent manner, and induce toxicity via both AHR-dependent and-independent mechanisms. PAH exposure is known to induce developmental malformations in zebrafish embryos, and recent studies have shown cardiac toxicity induced by compounds with low AHR affinity. Unraveling the potentially diverse molecular mechanisms of PAH toxicity is essential for understanding the hazard posed by complex PAH mixtures present in the environment. We analyzed transcriptional responses to PAH exposure in zebrafish embryos exposed to benz(a)anthracene (BAA), dibenzothiophene (DBT) and pyrene (PYR) at concentrations that induced developmental malformations by 120 hours post-fertilization (hpf). Whole genome microarray analysis of mRNA expression at 24 and 48 hpf identified genes that were differentially regulated over time and in response to the three PAH structures. PAH body burdens were analyzed at both time points using GC-MS, and demonstrated differences in PAH uptake into the embryos. This was important for discerning dose-related differences from those that represented unique molecular mechanisms. While BAA misregulated the least number of transcripts, it caused strong induction of cyp1a and other genes known to be downstream of the AHR, which were not induced by the other two PAHs. Analysis of functional roles of misregulated genes and their predicted regulatory transcription factors also distinguished the BAA response from regulatory networks disrupted by DBT and PYR exposure. These results indicate that systems approaches can be used to classify the toxicity of PAHs based on the networks perturbed following exposure, and may provide a path for unraveling the toxicity of complex PAH mixtures. PMID:23656968

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

PubMed

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

2012-10-02

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

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

NASA Astrophysics Data System (ADS)

Van Vaeck, L.; Van Cauwenberghe, K.

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

Raman spectroscopy detects biomolecular changes associated with nanoencapsulated hesperetin treatment in experimental oral carcinogenesis

NASA Astrophysics Data System (ADS)

Gurushankar, K.; Gohulkumar, M.; Kumar, Piyush; Krishna, C. Murali; Krishnakumar, N.

2016-03-01

Recently it has been shown that Raman spectroscopy possesses great potential in the investigation of biomolecular changes of tumor tissues with therapeutic drug response in a non-invasive and label-free manner. The present study is designed to investigate the antitumor effect of hespertin-loaded nanoparticles (HETNPs) relative to the efficacy of native hesperetin (HET) in modifying the biomolecular changes during 7,12-dimethyl benz(a)anthracene (DMBA)-induced oral carcinogenesis using a Raman spectroscopic technique. Significant differences in the intensity and shape of the Raman spectra between the control and the experimental tissues at 1800-500 cm-1 were observed. Tumor tissues are characterized by an increase in the relative amount of proteins, nucleic acids, tryptophan and phenylalanine and a decrease in the percentage of lipids when compared to the control tissues. Further, oral administration of HET and its nanoparticulates restored the status of the lipids and significantly decreased the levels of protein and nucleic acid content. Treatment with HETNPs showed a more potent antitumor effect than treatment with native HET, which resulted in an overall reduction in the intensity of several biochemical Raman bands in DMBA-induced oral carcinogenesis being observed. Principal component and linear discriminant analysis (PC-LDA), together with leave-one-out cross validation (LOOCV) on Raman spectra yielded diagnostic sensitivities of 100%, 80%, 91.6% and 65% and specificities of 100%, 65%, 60% and 55% for classification of control versus DMBA, DMBA versus DMBA  +  HET, DMBA versus DMBA  +  HETNPs and DMBA  +  HET versus DMBA  +  HETNPs treated tissue groups, respectively. These results further demonstrate that Raman spectroscopy associated with multivariate statistical algorithms could be a valuable tool for developing a comprehensive understanding of the process of biomolecular changes, and could reveal the signatures of the

Estimating individual-level exposure to airborne polycyclic aromatic hydrocarbons throughout the gestational period based on personal, indoor, and outdoor monitoring

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

Choi, H.; Perera, F.; Pac, A.

2008-11-15

Current understanding on health effects of long-term polycyclic aromatic hydrocarbon (PAH) exposure is limited by lack of data on time-varying nature of the pollutants at an individual level. In a cohort of pregnant women in Krakow, Poland, we examined the contribution of temporal, spatial, and behavioral factors to prenatal exposure to airborne PAHs within each trimester and developed a predictive model of PAH exposure over the entire gestational period. The observed personal, indoor, and outdoor B(a)P levels we observed in Krakow far exceed the recommended Swedish guideline value for B(a)P of 0.1 ng/m{sup 3}. Based on simultaneously monitored levels, themore » outdoor PAH level alone accounts for 93% of total variability in personal exposure during the heating season. Living near the Krakow bus depot, a crossroad, and the city, center and time spent outdoors or commuting were not associated with higher personal exposure. During the nonheating season only, a 1-hr increase in environmental tobacco smoke (ETS) exposure was associated with a 10-16% increase in personal exposure to the nine measured PAHs. A 1{degree}C decrease in ambient temperature was associated with a 3-5% increase in exposure to benz(a)anthracene, benzo(k)fluoranthene, and dibenz(a,h)anthracene, after accounting for the outdoor concentration. A random effects model demonstrated that mean personal exposure at a given gestational period depends on the season, residence location, and ETS. Considering that most women reported spending < 3 hr/day outdoors, most women in the study were exposed to outdoor-originating PAHs within the indoor setting. Cross-sectional, longitudinal monitoring supplemented with questionnaire data allowed development of a gestation-length model of individual-level exposure with high precision and validity.« less

Phthalate and PAH concentrations in dust collected from Danish homes and daycare centers

NASA Astrophysics Data System (ADS)

Langer, Sarka; Weschler, Charles J.; Fischer, Andreas; Bekö, Gabriel; Toftum, Jørn; Clausen, Geo

2010-06-01

As part of the Danish Indoor Environment and Children's Health (IECH) study, dust samples were collected from 500 bedrooms and 151 daycare centers of children (ages 3 to 5) living on the island of Fyn. The present paper reports results from the analyses of these samples for five phthalate esters (diethyl phthalate (DEP), di(n-butyl) phthalate (DnBP), di(isobutyl) phthalate (DiBP), butyl benzyl phthalate (BBzP), di(2-ethylhexyl) phthalate (DEHP)) and three PAHs (pyrene, benz[a]anthracene (B[a]A) and benzo[a]pyrene (B[a]P)). The three PAHs and DEHP were detected in dust samples from all sites, while DEP, DnBP, DiBP and BBzP were detected in more than 75% of the bedrooms and more than 90% of the daycare centers. The dust mass-fractions of both phthalates and PAHs were log-normally distributed. With the exception of DEP, the mass-fractions of phthalates in dust were higher in daycare centers than homes; PAH mass-fractions in dust were similar in the two locations. There was no correlation among the different phthalates in either homes or daycare centers. In contrast, the PAH were correlated with one another - more strongly so in homes ( R2 = 0.80-0.90) than in daycare centers ( R2 = 0.28-0.45). The dust levels of several phthalates (BBzP, DnBP and DEHP) were substantially lower than those measured in a comparable study conducted 6-7 years earlier in Sweden. Although usage patterns in Denmark differ from those in Sweden, the current results may also reflect a change in the plasticizers that are used in common products including toys. PAH levels were roughly an order of magnitude lower than those measured in Berlin and Cape Cod residences, suggesting that the Danish sites are less impacted by motor vehicle emissions.

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

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

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

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

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

PubMed

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

2013-06-14

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

Chemotherapeutic effect of tangeretin, a polymethoxylated flavone studied in 7, 12-dimethylbenz(a)anthracene induced mammary carcinoma in experimental rats.

PubMed

Lakshmi, A; Subramanian, S

2014-04-01

Globally, breast cancer is the second most prevalent cancer among women and its incidence is amplifying alarmingly. Since genetics is believed to account for only 10% of the reported cases, the environmental factors including diet are thought to play a significant role in predisposing breast cancer. Many bioactive compounds of plant origin have been reported for their anticancer potential. Tangeretin, a pentamethoxy flavone, is a naturally occurring phytoconstituent found to be present in significant amounts in the peel of citrus fruits. Tangeretin possess a wide array of pharmacological activities such as cytostatic, anti-proliferative and antioxidant properties. In the absence of systemic studies in the literature, the present study was aimed to evaluate the chemotherapeutic potential of tangeretin in 7, 12-dimethyl benz(a)anthracene (DMBA) induced mammary carcinoma in rats. Oral treatment of tangeretin (50 mg/kg BW) to breast tumor bearing rats daily for four weeks was found to be effective against DMBA induced mammary gland carcinogenesis in female Wistar rats. The increased activities of AST, ALT, ALP, ACP, 5'-ND, γ-GT and LDH in serum of control and experimental breast cancer rats were significantly (p < 0.05) decreased to near normal levels. Further, the levels of lipid peroxide (TBARS), enzymatic antioxidants such as SOD, CAT, GPx and non-enzymatic antioxidants such as GSH, Vitamin C, Vitamin E and Phase I (cytochrome P450, cytochrome b5, EROD, MROD and PROD) and Phase II detoxification (glutathione S-transferase (GST), quinone reductase (QR)) were decreased significantly by administration of tangeretin. Immunohistochemical and western blotting studies for estrogen receptor, progesterone receptor and HER2/neu status exemplified the chemotherapeutic effect of tangeretin. Further, the histological and ultrastructural analysis of breast tissues evidenced the anti-tumorigenic nature of tangeretin. Thus, the results of the present study clearly indicate that

The effect of dietary zinc - and polyphenols intake on DMBA-induced mammary tumorigenesis in rats

PubMed Central

2012-01-01

Background The aim of the study was to investigate the effect of dietary supplementation with zinc and polyphenol compounds, i.e. resveratrol and genistein, on the effectiveness of chemically induced mammary cancer and the changes in the content of selected elements (Zn, Cu, Mg, Fe, Ca) in tumors as compared with normal tissue of the mammary gland. Methods Female Sprague-Dawley rats were divided into study groups which, apart from the standard diet and DMBA (7,12-dimethyl-1,2- benz[a]anthracene), were treated with zinc ions (Zn) or zinc ions + resveratrol (Zn + resveratrol) or zinc ions + genistein (Zn + genistein) via gavage for a period from 40 days until 20 weeks of age. The ICP-OES (inductively coupled plasma optical emission spectrometry) technique was used to analyze the following elements: magnesium, iron, zinc and calcium. Copper content in samples was estimated in an atomic absorption spectrophotometer. Results Regardless of the diet (standard; Zn; Zn + resveratrol; Zn + genistein), DMBA-induced breast carcinogenesis was not inhibited. On the contrary, in the Zn + resveratrol supplemented group, tumorigenesis developed at a considerably faster rate. On the basis of quantitative analysis of selected elements we found - irrespectively of the diet applied - great accumulation of copper and iron, which are strongly prooxidative, with a simultaneous considerable decrease of the magnesium content in DMBA-induced mammary tumors. The combination of zinc supplementation with resveratrol resulted in particularly large differences in the amount of the investigated elements in tumors as compared with their content in normal tissue. Conclusions Diet supplementation with zinc and polyphenol compounds, i.e. resveratrol and genistein had no effect on the decreased copper level in tumor tissue and inhibited mammary carcinogenesis in the rat. Irrespectively of the applied diet, the development of the neoplastic process in rats resulted in changes of the iron and magnesium

Deviation from additivity in mixture toxicity: relevance of nonlinear dose-response relationships and cell line differences in genotoxicity assays with combinations of chemical mutagens and gamma-radiation.

PubMed

Lutz, Werner K; Vamvakas, Spyros; Kopp-Schneider, Annette; Schlatter, Josef; Stopper, Helga

2002-12-01

Sublinear dose-response relationships are often seen in toxicity testing, particularly with bioassays for carcinogenicity. This is the result of a superimposition of various effects that modulate and contribute to the process of cancer formation. Examples are saturation of detoxification pathways or DNA repair with increasing dose, or regenerative hyperplasia and indirect DNA damage as a consequence of high-dose cytotoxicity and cell death. The response to a combination treatment can appear to be supra-additive, although it is in fact dose-additive along a sublinear dose-response curve for the single agents. Because environmental exposure of humans is usually in a low-dose range and deviation from linearity is less likely at the low-dose end, combination effects should be tested at the lowest observable effect levels (LOEL) of the components. This principle has been applied to combinations of genotoxic agents in various cellular models. For statistical analysis, all experiments were analyzed for deviation from additivity with an n-factor analysis of variance with an interaction term, n being the number of components tested in combination. Benzo[a]pyrene, benz[a]anthracene, and dibenz[a,c]anthracene were tested at the LOEL, separately and in combination, for the induction of revertants in the Ames test, using Salmonella typhimurium TA100 and rat liver S9 fraction. Combined treatment produced no deviation from additivity. The induction of micronuclei in vitro was investigated with ionizing radiation from a 137Cs source and ethyl methanesulfonate. Mouse lymphoma L5178Y cells revealed a significant 40% supra-additive combination effect in an experiment based on three independent replicates for controls and single and combination treatments. On the other hand, two human lymphoblastoid cell lines (TK6 and WTK1) as well as a pilot study with human primary fibroblasts from fetal lung did not show deviation from additivity. Data derived from one cell line should therefore

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

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

The effect of zinc and phytoestrogen supplementation on the changes in mineral content of the femur of rats with chemically induced mammary carcinogenesis.

PubMed

Skrajnowska, Dorota; Korczak, Barbara Bobrowska-; Tokarz, Andrzej; Kazimierczuk, Agata; Klepacz, Marta; Makowska, Justyna; Gadzinski, Blazej

2015-10-01

The aim of this study was to assess skeletal effects of zinc or zinc with phytoestrogen (resveratrol or genistein) supplementation in an animal model of rats with DMBA-induced mammary carcinogenesis. The changes in bone parameters such as the length and mass were examined, as well as the changes in concentrations of selected minerals: calcium, magnesium, zinc, iron and phosphorus. Moreover, the investigations focused on finding the differences between the levels of iron and zinc in other tissues: the liver, spleen and serum of the examined rats. Fifty-six female Sprague-Dawley rats, 40 days old, were divided into four groups, regardless of the diets: standard (77mg Zn kg/food), zinc (4.6mg/mL via gavage), zinc (4.6mg/mL) plus resveratrol (0.2mg/kgbw), and zinc (4.6mg/mL) plus genistein (0.2mg/kgbw) for a period from 40 days until 20 weeks of age. The study rats were also treated with 7,12-dimethyl-1,2-benz[a]anthracene (DMBA) to induce mammary carcinogenesis. The applied diet and the advanced mammary cancer did not affect macrometric parameters of the rats' bones, but they strongly affected their mineral content. It was found that mammary cancer, irrespectively of the applied diet, significantly modified the iron level in the femur, liver, spleen and serum of the examined rats. In addition, zinc supplementation significantly lowered the levels of calcium, magnesium and phosphorus in the femur of rats with mammary cancer as compared with respective levels in the control group. So, it was found that additional supplementation with zinc, which is generally considered to be an antioxidant, with the co-existing mammary carcinoma, increased the unfavorable changes as concerns the stability of bone tissue. The appropriate combination of zinc and phytoestrogens (resveratrol or genistein) could help prevent or slow bone loss associated with a range of skeletal disorders in breast cancer. Copyright © 2015 Elsevier GmbH. All rights reserved.

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

PubMed

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

2016-06-01

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

Comparative developmental toxicity of environmentally relevant oxygenated PAHs

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

Knecht, Andrea L., E-mail: andrea.knecht@tanguaylab.com; Goodale, Britton C., E-mail: goodaleb@onid.orst.edu; Truong, Lisa, E-mail: lisa.truong.888@gmail.com

2013-09-01

Oxygenated polycyclic aromatic hydrocarbons (OPAHs) are byproducts of combustion and photo-oxidation of parent PAHs. OPAHs are widely present in the environment and pose an unknown hazard to human health. The developing zebrafish was used to evaluate a structurally diverse set of 38 OPAHs for malformation induction, gene expression changes and mitochondrial function. Zebrafish embryos were exposed from 6 to 120 h post fertilization (hpf) to a dilution series of 38 different OPAHs and evaluated for 22 developmental endpoints. AHR activation was determined via CYP1A immunohistochemistry. Phenanthrenequinone (9,10-PHEQ), 1,9-benz-10-anthrone (BEZO), xanthone (XAN), benz(a)anthracene-7,12-dione (7,12-B[a]AQ), and 9,10-anthraquinone (9,10-ANTQ) were evaluated for transcriptionalmore » responses at 48 hpf, prior to the onset of malformations. qRT-PCR was conducted for a number of oxidative stress genes, including the glutathione transferase(gst), glutathione peroxidase(gpx), and superoxide dismutase(sod) families. Bioenergetics was assayed to measure in vivo oxidative stress and mitochondrial function in 26 hpf embryos exposed to OPAHs. Hierarchical clustering of the structure-activity outcomes indicated that the most toxic of the OPAHs contained adjacent diones on 6-carbon moieties or terminal, para-diones on multi-ring structures. 5-carbon moieties with adjacent diones were among the least toxic OPAHs while the toxicity of multi-ring structures with more centralized para-diones varied considerably. 9,10-PHEQ, BEZO, 7,12-B[a]AQ, and XAN exposures increased expression of several oxidative stress related genes and decreased oxygen consumption rate (OCR), a measurement of mitochondrial respiration. Comprehensive in vivo characterization of 38 structurally diverse OPAHs indicated differential AHR dependency and a prominent role for oxidative stress in the toxicity mechanisms. - Highlights: • OPAHs are byproducts of combustion present in the environment. • OPAHs pose a

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

PubMed

Bieniek, Grażyna; Łusiak, Agnieszka

2012-08-01

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

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

PubMed

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

2014-03-01

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

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

PubMed

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

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Hydrologic and Water-Quality Responses in Shallow Ground Water Receiving Stormwater Runoff and Potential Transport of Contaminants to Lake Tahoe, California and Nevada, 2005-07

USGS Publications Warehouse

Green, Jena M.; Thodal, Carl E.; Welborn, Toby L.

2008-01-01

all less than laboratory reporting limits in the deeper sediment sample, but 15 compounds were detected in the uppermost 0.2 foot of sediment. Published concentrations determined to affect benthic aquatic life also were exceeded for copper, zinc, benz[a]anthracene, phenanthrene, and pyrene in the shallow sediment sample. Isotopic composition of water (oxygen 18/16 and hydrogen 2/1 ratios) for samples of shallow ground water, lakewater, and interstitial water from Lake Tahoe indicate the lake was well mixed with a slight ground-water signature in samples collected near the lakebed. One interstitial sample from 0.8 foot beneath the lakebed was nearly all ground water and concentrations of nitrogen and phosphorus were comparable to concentrations in shallow ground-water samples. However, ammonium represented 65 percent of filtered nitrogen in this interstitial sample, but only 10 percent of the average nitrogen in ground-water samples. Nitrate was less than reporting limits in interstitial water, compared with mean nitrate concentration of 750 micrograms per liter in ground-water samples, indicating either active dissimilative nitrate reduction to ammonium by micro-organisms or hydrolysis of organic nitrogen to ammonium with concomitant nitrate reduction. The other interstitial sample falls along a mixing line between ground water and lake water and most of the nitrogen was organic nitrogen.

Water-Quality Conditions of Chester Creek, Anchorage, Alaska, 1998-2001

USGS Publications Warehouse

Glass, Roy L.; Ourso, Robert T.

2006-01-01

, tetrachloroethylene, methyl tert-butyl ether, and chloroform. No water samples contained volatile organic compounds concentrations that exceeded any USEPA drinking-water standard or guideline. Fecal-indicator bacteria concentrations in water from the Arctic Boulevard site commonly exceeded Federal and State guidelines for water-contact recreation. Concentrations of cadmium, copper, lead, and zinc in streambed sediments increased in the downstream direction. Some concentrations of arsenic, chromium, lead, and zinc in sediments were at levels that can adversely affect aquatic organisms. Analysis of sediment chemistry in successive lakebed-sediment layers from Westchester Lagoon near the stream's mouth provided a record of water-quality trends since about 1970. Concentrations of lead have decreased from peak levels in the mid-1970s, most likely because of removing lead from gasoline and lower lead content in other products. However, concen-trations in recently-deposited lakebed sediments are still about 10 times greater than measured in streambed sediments at the upstream Tank Trail site. Zinc concentrations in lakebed sediments also increased in the early 1970s to levels that exceeded guidelines to protect aquatic life and have remained at elevated but variable levels. Pyrene, benz[a]anthracene, and phenanthrene in lakebed sediments also have varied in concentrations and have exceeded protection guidelines for aquatic life since the 1970s. Concentrations of dichloro-diphenyl-trichloroethane, polychlorinated biphenyls (PCBs), or their by-products generally were highest in lakebed sediments deposited in the 1970s. More recent sediments have concentrations that vary widely and do not show distinct temporal trends. Tissue samples of whole slimy sculpin (Cottus cognatus), a non-migratory species of fish, showed con-centrations of trace elements and organic contaminants. Of the constituents analyzed, only selenium concentra-tions showed levels of potential concern for

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

USGS Publications Warehouse

Rachol, Cynthia M.; Button, Daniel T.

2006-01-01

were collected throughout the lake. The distribution of trace-element concentrations corresponded well with the results of a two-dimensional hydrodynamic model of flow patterns from the Clinton River into Lake St. Clair. The model was developed independent from the bed sediment analysis described in this report; yet it showed a zone of deposition for outflow from the Clinton River into Lake St. Clair that corresponded well with the spatial distribution of trace-element concentrations. This zone runs along the western shoreline of Lake St. Clair from L'Anse Creuse Bay to St. Clair Shores, Michigan and is reflected in the samples analyzed for mercury and cadmium.Statistical summaries of the concentration data are presented for most contaminants, and selected statistics are compared to effects-based sediment-quality guidelines. Summaries were not computed for dieldrin, chlordane, hexachlorocyclohexane, lindane, and mirex because insufficient data are available for these contaminants. A statistical comparison showed that the median concentration for hexachlorobenzene, anthracene, benz[a]anthracene, chrysene, and pyrene are greater than the Threshold Effect Concentration or Lowest Effect Level.Probable Effect Concentration Quotients provide a mechanism for comparing the concentrations of contaminant mixtures against effects-based biota data. Probable Effect Concentration Quotients were calculated for individual samples and compared to effects-based toxicity ranges. The toxicity-range categories used in this study were nontoxic (quotients < 0.5) and toxic (quotients > 0.5). Of the 546 individual samples for which Probable Effect Concentration Quotients were calculated, 469 (86 percent) were categorized as being nontoxic and 77 (14 percent) were categorized as being toxic. Bed-sediment samples with toxic Probable Effect Concentration Quotients were collected from Paint Creek, Galloway Creek, the main stem of the Clinton River, Big Beaver Creek, Red Run, Clinton River towards

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

NASA Astrophysics Data System (ADS)

Zimmermann, Kathryn Jean

Nitrated polycyclic aromatic hydrocarbon (nitro-PAH) product distributions from the gas-phase hydroxyl (OH) and nitrate (NO3) radical-initiated reactions with selected PAHs, as well as the heterogeneous reactions of surface-bound PAHs with N2O5 and HNO3, were investigated. Chapter 2 presents formation yields of nitro-PAHs from the gas-phase OH radical-initiated reactions of 1,7- and 2,7-dimethylnaphthalene (DMN) as a function of NO 2 concentration over the range 0.04-0.14 ppmv. The measured formation yields of dimethylnitronaphthalenes (DMNNs) under conditions that the OH-DMN adducts reacted solely with NO2 were 0.252 ± 0.094% for Σ1,7-DMNNs and 0.010 ± 0.005% for Σ2,7-DMNNs. 1,7-dimethyl-5-nitronaphthalene (1,7DM5NN) was the major nitro-isomer formed, with a limiting high-NO 2 concentration yield of 0.212 ± 0.080% and with equal reactions of the 1,7-DMN-OH adduct with NO2 and O2 occurring in air at 60 ± 39 ppbv of NO2, indicating that the OH-DMN adduct reaction with NO2 can be important at NO2 concentrations commonly found in urban atmospheres. Although the yields of the DMNNs are low, ≤0.3%, the DMNN (and ethylnitronaphthalene) profiles from chamber experiments match well with those observed in polluted urban areas under conditions where OH radical-initiated chemistry is dominant, such as Mexico City, Mexico. Chapter 3 examines the nitro-PAH products of gas-phase OH and NO 3 radicals and heterogeneous N2O5 reactions with fluoranthene, pyrene, benz[a]anthracene, chrysene, and triphenylene. Analysis of nitro-PAHs in the NIST diesel particulate SRM (1975) and selected ambient samples are also presented. 2-Nitrofluoranthene (2-NFL) was the most abundant nitro-PAH in Riverside, CA and Mexico City, and the mw 273 nitro-PAHs were observed in lower concentrations. However, in Tokyo, Japan, concentrations of 1- + 2-nitrotriphenylene (NTP) were more similar to those of 2-NFL. Comparing specific nitro-PAH ratios in ambient particulate samples from Tokyo, Mexico City