421 resultados para PAH
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The biotransformation of the polycyclic aromatic hydrocarbons (PAHs) naphthalene and phenanthrene was investigated by using two dioxygenase-expressing bacteria, Pseudomonas sp. strain 9816/11 and Sphingomonas yanoikuyae B8/36, under conditions which facilitate mass-transfer limited substrate oxidation. Both of these strains are mutants that accumulate cis-dihydrodiol metabolites under the reaction conditions used. The effects of the nonpolar solvent 2,2,4,4,6,8,8-heptamethylnonane (HMN) and the nonionic surfactant Triton X-100 on the rate of accumulation of these metabolites were determined. HMN increased the rate of accumulation of metabolites for both microorganisms, with both substrates. The enhancement effect was most noticeable with phenanthrene, which has a lower aqueous solubility than naphthalene. Triton X-100 increased the rate of oxidation of the PAHs with strain 9816/11 with the effect being most noticeable when phenanthrene was used as a substrate. However, the surfactant inhibited the biotransformation of both naphthalene and phenanthrene with strain B8/36 under the same conditions. The observation that a nonionic surfactant could have such contrasting effects on PAH oxidation by different bacteria, which are known to be important for the degradation of these compounds in the environment, may explain why previous research on the application of the surfactants to PAH bioremediation has yielded inconclusive results. The surfactant inhibited growth of the wild-type strain S. yanoikuyae B1 on aromatic compounds but did not inhibit B8/36 dioxygenase enzyme activity in vitro.
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Galactic bulge planetary nebulae show evidence of mixed chemistry with emission from both silicate dust and PAHs. This mixed chemistry is unlikely to be related to carbon dredge up, as third dredge-up is not expected to occur in the low mass bulge stars. We show that the phenomenon is widespread, and is seen in 30 nebulae out of our sample of 40. A strong correlation is found between strength of the PAH bands and morphology, in particular, the presence of a dense torus. A chemical model is presented which shows that hydrocarbon chains can form within oxygen-rich gas through gas-phase chemical reactions. We conclude that the mixed chemistry phenomenon occurring in the galactic bulge planetary nebulae is best explained through hydrocarbon chemistry in an UV-irradiated, dense torus. © 2012 International Astronomical Union.
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This paper reports variations of polycyclic aromatic hydrocarbons (PAHs) features that were found in Spitzer Space Telescope spectra of carbon-rich post-asymptotic giant branch (post-AGB) stars in the Large Magellanic Cloud (LMC). The paper consists of two parts. The first part describes our Spitzer spectral observing programme of 24 stars including post-AGB candidates. The latter half of this paper presents the analysis of PAH features in 20 carbon-rich post-AGB stars in the LMC, assembled from the Spitzer archive as well as from our own programme.We found that five post-AGB stars showed a broad feature with a peak at 7.7 μm, that had not been classified before. Further, the 10-13 μm PAH spectra were classified into four classes, one of which has three broad peaks at 11.3, 12.3 and 13.3 μm rather than two distinct sharp peaks at 11.3 and 12.7 μm, as commonly found in HII regions. Our studies suggest that PAHs are gradually processed while the central stars evolve from post-AGB phase to planetary nebulae, changing their composition before PAHs are incorporated into the interstellar medium. Although some metallicity dependence of PAH spectra exists, the evolutionary state of an object is more significant than its metallicity in determining the spectral characteristics of PAHs for LMC and Galactic post-AGB stars. © 2014 The Authors Published by Oxford University Press on behalf of the Royal Astronomical Society.
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We compare a suite of Polycyclic Aromatic Hydrocarbons (Parent PAHs) in soils and air across an urban area (Belfast UK). Isomeric PAH ratios suggest that soil PAHs are mainly from a combustion source. Fugacity modelling across a range of soil temperatures predicts that four ring and larger PAHs from pyrene to indeno[1,2,3–cd]pyrene all partition strongly (>98%) to the soil compartment. This modelling also implies that these PAHs do not experience losses through partitioning to other phases (air, water) due to soil temperature effects. Such modelling may help in understanding the overall contaminantdistribution in soils. The air and soil data together with modelling suggests that care must be taken when considering isomeric ratios of compounds with mass lighter than 178 (i.e. phenanthrene and anthracene) in the soil phase. Comparison of duplicate and replicate samples suggest that field sampling of duplicates dominates uncertainty and validated methodologies for selection of field duplicates and lab splitting are required. As the urban soil four ring PAHs are at equilibrium in the soil phase, and have characteristic ratios that are dominated by a combustion source that is a single controlling factor over spatial distribution, methods that calculate background concentrations can be compared.
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A new technological approach in the analysis and forensic interpretation of Total Hydrocarbons in soils and waters using 2D Gas Chromatography method (GC-GC) was developed alongside environmental forensic and the assessment models to provide better customer products for the environmental industry.
The objective was to develop an analytical methodology for TPH CWG. Raw data from this method is then to be evaluated for forensic interpretation and risk assessment modelling. Access will be made available to the expertise in methods of forensic tracing contaminant sources, transport modelling, human health risk modelling and detailed quantitative risk assessment.
The quantification of internal standards was key to the development of this method. As the laboratory does not test for TPH in 1D, it was requested during INAB ISO 17025 audit to individually map out where each compound falls chromatographically in the 2D. This was done through comparing carbon equivalent numbers to the n-alkane carbons. This proved e.g. 2-methylnaphthalene has 11 carbons in its structure; its carbon equivalent is 12.84 , the result of which falls within the band of Aromatic eC12-eC16 as opposed to expected eC10-eC12. This was carried out for all 16 PAH (polyaromatic hydrocarbons) and BTEX (benzene, toluene, ethylbenzene and o, m and p-xylenes). The n-alkanes were also assigned to their corresponding aliphatic bands e.g. nC8 would be expected to be in nC8-nC10.
The method was validated through a designated systematic experimental protocol and was challenged with spikes of known concentration of hydrocarbon parameters such as recoveries, precision, bias and linearity. The method was verified by testing a certified reference material which was used as a proficiency round of testing for numerous laboratories.
It is hoped that the method will be used in conjunction with the analysis through Bonn Agreement with their OSINet group. This is a panel of experts and laboratories (including CLS) who forensically identify oil spill contamination from a water source.
This method can prove itself to be a robust method and benefit the industry for contaminated land and water but the method needs to be seen as separate from the regular 1D chromatography. It will help identify contaminants and assist consultants, regulators, clients and scientists valuable information not seen in 1D
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No presente trabalho, foi estudado um largo espectro de efeitos genotóxicos e bioquímicos na tainha-garrento (Liza aurata). Nos Capítulos II e III são descritos os efeitos de exposição de curta duração ao fenantreno, um hidrocarboneto aromático policíclico (HAP). A exposição de curta duração (16 horas) demonstrou a capacidade deste composto induzir a actividade da enzima de fase I da biotransformação, etoxiresorufina O-desetilase (EROD), provocar decréscimos de integridade no ADN hepático e aumento de anomalias nucleares eritrocíticas (ANE). Em termos de respostas de stresse, os níveis plasmáticos de cortisol e glucose aumentaram face à exposição a este HAP. A exposição ao fenantreno induziu o decréscimo da glutationa peroxidase (GPx) nas guelras, enquanto que no fígado a actividade da GPx aumentou. No rim, a actividade da glutationa S-transferase (GST) foi inibida. Nas guelras, verificou-se um aumento da catalase. O fenantreno demonstrou igualmente a capacidade de induzir um aumento dos níveis de glutationa nas guelras e fígado. Estas respostas demonstraram a sensibilidade de L. aurata, a este HAP, realçando a especificidade das respostas em termos de órgãos. Apesar dos aumentos das defesas antioxidantes, o potencial tóxico deste composto foi demonstrado pelo aumento da peroxidação lipídica nos três órgãos. Nos capítulos seguintes, são descritas as respostas de L. aurata capturada na Ria de Aveiro, em locais com diferentes perfis de contaminação, inicialmente no Outono de 2005 (Capítulos III a IX) e posteriormente analisando respostas sazonais (Capítulos X e XI). A análise de respostas de stresse (cortisol, glucose e lactato) revelou que L. aurata capturada em Vagos (local contaminado por HAPs) apresentava níveis baixos de cortisol, enquanto que no Laranjo (local contaminado por mercúrio) apresentavam elevados níveis de glucose e lactato. Relativamente às hormonas do eixo hipotálamo – hipófise – tiróide (HHT), foram observados elevados níveis plasmáticos da hormona estimuladora da tiróide (TSH) nos organismos capturados no Laranjo, baixos níveis de tiroxina (T4) nos organismos da Barra (local sujeito a tráfego naval) e baixos níveis de triiodotironina (T3) no Rio Novo do Príncipe (próximo de um antigo efluente de pasta de papel), Laranjo e Vagos. A avaliação das defesas antioxidantes, dano oxidativo e genotóxico nas guelras, rim e fígado revelou diferenças significativas nas respostas dos órgãos. L. aurata capturada na Barra apresentou dano oxidativo nas guelras (Capítulo V). No rim foi detectada uma diminuição da integridade do ADN no Rio Novo do Príncipe e Vagos (Capítulo VI), enquanto que no fígado foi observado dano lipídico na Gafanha e Vagos (Capítulo VIII). O dano não esteve sempre associado a um decréscimo das defesas. As análises da água e do sedimento da Ria de Aveiro (Outono de 2005) revelaram elevadas concentrações de metais (Cd, Hg, Cu e Zn),principalmente, no Laranjo e Rio Novo do Príncipe. L. aurata capturada nestes locais apresentou os níveis mais elevados de metalotioninas hepáticas (Capítulo VII) que parecem responsáveis pela inexistência de danos no fígado (Capítulo VIII). O dano oxidativo no ADN, avaliado através da quantificação dos níveis plasmáticos de 8-hidroxi-2-desoxiguanosina (8-OHdG) e o dano clastogénico/aneugénico, avaliado através da quantificação da frequência de ANE, foram estudados, no Outono de 2005, em duas espécies de peixes (L. aurata e Dicentrarchus labrax - robalo) (Capítulo IX). Os resultados revelaram grande sensibilidade de D. labrax em termos de dano oxidativo no ADN na Gafanha, Rio Novo do Príncipe e Vagos, enquanto que L. aurata apresentou dano oxidativo apenas no Laranjo. O aumento da frequência de ANE apenas foi detectado em L. aurata, em Vagos, não se tendo detectado correlação entre estes dois parâmetros. O estudo sazonal (Maio de 2006 a Março de 2007) do dano oxidativo no ADN e frequência de ANE em L. aurata (Capítulo X) demonstrou a variação destes parâmetros com a estação do ano, apesar de não se ter verificado correlação com os parâmetros hidrológicos determinados. No entanto, no local de referência não se verificaram diferenças sazonais, o que sugere que estes biomarcadores reflectem variações de biodisponibilidade de contaminantes. A análise global dos resultados das diferentes estações do ano revelou que L. aurata capturada no Rio Novo do Príncipe e em Vagos apresentou maior susceptibilidade a dano oxidativo no ADN. No entanto, apenas L. aurata capturada em Vagos apresentou frequência de ANE superior à do local de referência. Os dados do estudo sazonal revelaram uma correlação entre dano oxidativo e ANE, sugerindo o stresse oxidativo como um possível mecanismo envolvido na formação de anomalias. A integridade do ADN das guelras, rim, fígado e sangue de L. aurata foi igualmente estudada ao longo de um ano (Capítulo XI), tendo-se verificado uma grande variabilidade ao longo deste período. Não foi demonstrada sensibilidade a um perfil de contaminação específico, tendo-se verificando variabilidade sazonal no local de referência. Globalmente, os resultados demonstraram a importância da utilização de uma bateria de biomarcadores na monitorização ambiental e a especificidade da resposta dos diferentes órgãos de L. aurata.
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Salt marshes are highly productive intertidal habitats that serve as nursery grounds for many commercially and economically important species. Because of their location and physical and biological characteristics, salt marshes are considered to be particularly vulnerable to anthropogenic inputs of oil hydrocarbons. Sediment contamination with oil is especially dangerous for salt marsh vegetation, since low molecular weight aromatic hydrocarbons can affect plants at all stages of development. However, the use of vegetation for bioremediation (phytoremediation), by removal or sequestration of contaminants, has been intensively studied. Phytoremediation is an efficient, inexpensive and environmental friendly approach for the removal of aromatic hydrocarbons, through direct incorporation by the plant and by the intervention of degrading microbial populations in the rhizosphere (microbe-assisted phytoremediation). Rhizosphere microbial communities are enriched in important catabolic genotypes for degradation of oil hydrocarbons (OH) which may have a potential for detoxification of the sediment surrounding the roots. In addition, since rhizosphere bacterial populations may also internalize into plant tissues (endophytes), rhizocompetent AH degrading populations may be important for in planta AH degradation and detoxification. The present study involved field work and microcosms experiments aiming the characterization of relevant plant-microbe interactions in oilimpacted salt marshes and the understanding of the effect of rhizosphere and endosphere bacteria in the role of salt marsh plants as potential phytoremediation agents. In the field approach, molecular tools were used to assess how plant species- and OH pollution affect sediment bacterial composition [bulk sediment and sediment surrounding the roots (rhizosphere) of Halimione portulacoides and Sarcocornia perennis subsp. perennis] in a temperate estuary (Ria de Aveiro, Portugal) chronically exposed to OH pollution. In addition, the 16S rRNA gene sequences retrieved in this study were used to generate in silico metagenomes and to evaluate the distribution of potential bacterial traits in different microhabitats. Moreover, a combination of culture-dependent and -independent approaches was used to investigate the effect of oil hydrocarbons contamination on the structure and function of endophytic bacterial communities of salt marsh plants.Root systems of H. portulacoides and S. perennis subsp. perennis appear to be able to exert a strong influence on bacterial composition and in silico metagenome analysis showed enrichment of genes involved in the process of polycyclic aromatic hydrocarbon (PAH) degradation in the rhizosphere of halophyte plants. The culturable fraction of endophytic degraders was essentially closely related to known OH-degrading Pseudomonas species and endophytic communities revealed sitespecific effects related to the level of OH contamination in the sediment. In order to determine the effects of oil contamination on plant condition and on the responses in terms of structure and function of the bacterial community associated with plant roots (rhizosphere, endosphere), a microcosms approach was set up. The salt marsh plant Halimione portulacoides was inoculated with a previous isolated Pseudomonas sp. endophytic degrader and the 2-methylnaphthalene was used as model PAH contaminant. The results showed that H. portulacoides health and growth were not affected by the contamination with the tested concentration. Moreover, the decrease of 2-methylnaphthalene at the end of experiment, can suggest that H. portulacoides can be considered as a potential plant for future uses in phytoremedition approaches of contaminated salt marsh. The acceleration of hydrocarbon degradation by inoculation of the plants with the hydrocarbon-degrading Pseudomonas sp. could not, however, be demonstrated, although the effects of inoculation on the structure of the endophytic community observed at the end of the experiment indicate that the strain may be an efficient colonizer of H. portulacoides roots. The results obtained in this work suggest that H. portulacoides tolerates moderate concentrations of 2-methylnaphthalene and can be regarded as a promising agent for phytoremedition approaches in salt marshes contaminated with oil hydrocarbons. Plant/microbe interactions may have an important role in the degradation process, as plants support a diverse endophytic bacterial community, enriched in genetic factors (genes and plasmids) for hydrocarbon degradation.
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Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014
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Bacterial food poisoning is an ever-present threat that can be prevented with proper care and handling of food products. A disposable electrochemical immunosensor for the simultaneous measurements of common food pathogenic bacteria namely Escherichia coli O157:H7 (E. coli), campylobacter and salmonella were developed. The immunosensor was fabricated by immobilizing the mixture of anti-E. coli, anticampylobacter and anti-salmonella antibodies with a ratio of 1:1:1 on the surface of the multiwall carbon nanotube-polyallylamine modified screen printed electrode (MWCNT-PAH/SPE). Bacteria suspension became attached to the immobilized antibodies when the immunosensor was incubated in liquid samples. The sandwich immunoassay was performed with three antibodies conjugated with specific nanocrystal ( -E. coli-CdS, -campylobacter-PbS and -salmonella-CuS) which has releasable metal ions for electrochemical measurements. The square wave anodic stripping voltammetry (SWASV) was employed to measure released metal ions from bound antibody nanocrystal conjugates. The calibration curves for three selected bacteria were found in the range of 1 × 103 – 5 × 105 cells mL−1 with the limit of detection (LOD) 400 cells mL−1 for salmonella, 400 cells mL−1 for campylobacter and 800 cells mL−1 for E. coli. The precision and sensitivity of this method show the feasibility of multiplexed determination of bacteria in milk samples.
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Air pollution represents a serious risk not only to environment and human health, but also to historical heritage. In this study, air pollution of the Oporto Metropolitan Area and its main impacts were characterized. The results showed that levels of CO, PM10 and SO2 have been continuously decreasing in the respective metropolitan area while levels of NOx and NO2 have not changed significantly. Traffic emissions were the main source of the determined polycyclic aromatic hydrocarbons (PAHs; 16 PAHs considered by U.S. EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in air of the respective metropolitan area. The mean concentration of 18 PAHs in air was 69.9±39.7 ng m−3 with 3–4 rings PAHs accounting for 75% of the total ΣPAHs. The health risk analysis of PAHs in air showed that the estimated values of lifetime lung cancer risks considerably exceeded the health-based guideline level. Analytical results also confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere. FTIR and EDX analyses showed that gypsum was the most important constituent of black crusts of the characterized historical monument Monastery of Serra do Pilar classified as “UNESCO World Cultural Heritage”. In black crusts, 4–6 rings compounds accounted approximately for 85% of ΣPAHs. The diagnostic ratios confirmed that traffic emissions were the major source of PAHs in black crusts; PAH composition profiles were very similar for crusts and PM10 and PM2.5.
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Purpose Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds commonly found as soil contaminants. Fungal degradation is considered as an environmentally friendly and cost-effective approach to remove PAHs from soil. Acenaphthylene (Ace) and Benzo[a]anthracene (BaA) are two PAHs that can coexist in soils; however, the influence of the presence of each other on their biodegradation has not been studied. The biodegradation of Ace and BaA, alone and in mixtures, by the white rot fungus Pleurotus ostreatus was studied in a sandy soil. Materials and methods Experimental microcosms containing soil spiked with different concentrations of Ace and BaAwere inoculated with P. ostreatus. Initial (t 0) and final (after 15 days of incubation) soil concentrations of Ace and BaA were determined after extraction of the PAHs. Results and discussion P. ostreatus was able to degrade 57.7% of the Ace in soil spiked at 30 mg kg−1 dry soil and 65.8% of Ace in soil spiked at 60 mg kg−1 dry soil. The degradation efficiency of BaA by P. ostreatus was 86.7 and 77.4% in soil spiked with Ace at 30 and 60 mg kg−1 dry soil, respectively. After 15 days of incubation, there were no significant differences in Ace concentration between soil spiked with Ace and soil spiked with Ace + BaA, irrespective of the initial soil concentration of both PAHs. There were also no differences in BaA concentration between soil spiked with BaA and soil spiked with BaA + Ace. Conclusions The results indicate that the fungal degradation of Ace and BaA was not influenced by the presence of each other’s PAH in sandy soil. Bioremediation of soils contaminated with Ace and BaA using P. ostreatus is a promising approach to eliminate these PAHs from the environment.
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Among organic pollutants existing in coastal areas, polycyclic aromatic hydrocarbons (PAHs) are of great concern due to their ubiquity and carcinogenic potential. The aim of this study was to evaluate the seasonal patterns of PAHs in the digestive gland and arm of the common octopus (Octopus vulgaris) from the Northwest Atlantic Portuguese coast. In the different seasons, 18 PAHs were determined and the detoxification capacity of the species was evaluated. Ethoxyresorufin O-deethylase (EROD) and ethoxycoumarin O-deethylase (ECOD) activities were measured to assess phase I biotransformation capacity. Individual PAH ratios were used for major source (pyrolytic/petrogenic) analysis. Risks for human consumption were determined by the total toxicity equivalence approach. Generally, low levels of PAHs were detected in the digestive gland and in the arm of octopus, with a predominance of low molecular over high molecular weight compounds. PAHs exhibited seasonality in the concentrations detected and in their main emission sources. In the digestive gland, the highest total PAH levels were observed in autumn possibly related to fat availability in the ecosystem and food intake. The lack of PAH elimination observed in the digestive gland after captivity could be possibly associated to a low biotransformation capacity, consistent with the negligible/undetected levels of EROD and ECOD activity in the different seasons. The emission sources of PAHs found in the digestive gland varied from a petrogenic profile observed in winter to a pyrolytic pattern in spring. In the arm, the highest PAH contents were observed in June; nevertheless, levels were always below the regulatory limits established for food consumption. The carcinogenic potential calculated for all the sampling periods in the arm were markedly lower than the ones found in various aquatic species from different marine environments. The results presented in this study give relevant baseline data for environmental monitoring of organic pollution in coastal areas.
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Sorption is commonly agreed to be the major process underlying the transport and fate of polycyclic aromatic hydrocarbons (PAHs) in soils. However, there is still a scarcity of studies focusing on spatial variability at the field scale in particular. In order to investigate the variation in the field of phenanthrene sorption, bulk topsoil samples were taken in a 15 × 15-m grid from the plough layer in two sandy loam fields with different texture and organic carbon (OC) contents (140 samples in total). Batch experiments were performed using the adsorption method. Values for the partition coefficient K d (L kg−1) and the organic carbon partition coefficient K OC (L kg−1) agreed with the most frequently used models for PAH partitioning, as OC revealed a higher affinity for sorption. More complex models using different OC compartments, such as non-complexed organic carbon (NCOC) and complexed organic carbon (COC) separately, performed better than single K OC models, particularly for a subset including samples with Dexter n < 10 and OC <0.04 kg kg−1. The selected threshold revealed that K OC-based models proved to be applicable for more organic fields, while two-component models proved to be more accurate for the prediction of K d and retardation factor (R) for less organic soils. Moreover, OC did not fully reflect the changes in phenanthrene retardation in the field with lower OC content (Faardrup). Bulk density and available water content influenced the phenanthrene transport mechanism phenomenon.
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This work aims to characterize levels and phase distribution of polycyclic aromatic hydrocarbons (PAHs) in indoor air of preschool environment and to assess the impact of outdoor PAH emissions to indoor environment. Gaseous and particulate (PM1 and PM2.5) PAHs (16 USEPA priority pollutants, plus dibenzo[a,l]pyrene, and benzo[j]fluoranthene) were concurrently sampled indoors and outdoors in one urban preschool located in north of Portugal for 35 days. The total concentration of 18 PAHs (ΣPAHs) in indoor air ranged from 19.5 to 82.0 ng/m3; gaseous compounds (range of 14.1–66.1 ng/m3) accounted for 85% ΣPAHs. Particulate PAHs (range 0.7–15.9 ng/m3) were predominantly associated with PM1 (76% particulate ΣPAHs) with 5-ring PAHs being the most abundant. Mean indoor/outdoor ratios (I/O) of individual PAHs indicated that outdoor emissions significantly contributed to PAH indoors; emissions from motor vehicles and fuel burning were the major sources.
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Occupational exposures to wood dust have been associated with an elevated risk of sinonasal cancer (SNC). Wood dust is recognized as a human carcinogen but the specific cancer causative agent remains unknown. One possible explanation is a co-exposure to; wood dust and polycyclic aromatic hydrocarbons (PAHs). PAHs could be generated during incomplete combustion of wood due to heat created by use of power tools. To determine if PAHs are generated from wood during common wood working operations, PAH concentrations in wood dust samples collected in an experimental chamber operated under controlled conditions were analyzed. In addition, personal air samples from workers exposed to wood dust (n = 30) were collected. Wood dust was generated using three different power tools: vibrating sander, belt sander, and saw; and six wood materials: fir, Medium Density Fiberboard (MDF), beech, mahogany, oak and wood melamine. Monitoring of wood workers was carried out by means of personal sampler device during wood working operations. We measured 21 PAH concentrations in wood dust samples by capillary gas chromatography-ion trap mass spectrometry (GC-MS). Total PAH concentrations in wood dust varied greatly (0.24-7.95 ppm) with the lowest being in MDF dust and the highest in wood melamine dust. Personal PAH exposures were between 37.5-119.8 ng m(-3) during wood working operations. Our results suggest that PAH exposures are present during woodworking operations and hence could play a role in the mechanism of cancer induction related to wood dust exposure.