Synchronous scanning phosphorimetry for the selective determination of chrysene: a metrological study

Room-temperature phosphorimetry was used to quantify trace levels of chrysene in sugar-cane spirits and in fish bile. A selective phosphorescence enhancer (AgNO3) and synchronous scanning allowed the detection of ng amounts of chrysene. Accuracy (113 ± 17%) and selectivity was evaluated using the CRM-NIST-1647d - Priority Pollutant Polycyclic Aromatic Hydrocarbons in acetonitrile. Analysis of sugar-cane spirit samples enabled recovery of 108 ± 18% which agreed with the one achieved using HPLC. Method's uncertainty was equivalent to 3.4 ng of the analyte, however, the analyte pre-concentration (SPE) improved sensibility and minimized the relative uncertainty. Characterization and homogeneity studies in fish bile were also performed.

Observation of the rare chrysene excimer

Formation of the so far elusive chrysene excimer in solution is achieved by using DNA as a supramolecular scaffold. Oligonucleotides possessing one or two chrysene building blocks have been synthesized. Chrysene excimer fluorescence has been unambiguously observed in DNA double strands, as well as in single strands containing two neighbouring chrysenes.

Formation of supramolecular polymers by chrysene oligomers

Supramolecular assembly of π-conjugated systems is of large interested due to the possibility to use them in electronic devices.[1] Chrysene is a polyaromatic hydrocarbon which has been studied e.g for organic light-emitting diodes (OLEDs).[2] In continuation of our previous work involving the supramolecular polymerisation of pyrene oligomers [3] an oligomer consisting of three chrysenes linked by phophodiesters was synthesised (Chry3). UV-Vis measurements show that aggregates of Chry3 are formed in aqueous medium. This is illustrated by general hypochromicity, a change in vibronic band intensities and, in particular, the appearance of a red-shifted absorption band in the S0 → S2 transition. The data suggest the formation of J-aggregates. The formation of supramolecular polymers is further studied by temperature-dependent absorption- and fluorescence measurements, and by atomic force microscopy (AFM).

Recherches sur la constitution du chrysene /

Thesis (doctoral)--Universite de Geneve, 1894.

Hidrocarbonetos aromáticos policíclicos em margarina, creme vegetal e maionese

Polycyclic aromatic hydrocarbons (PAHs) are a group of compounds that have been the subject of much concern due to their toxic potential. In this study, margarine?s, vegetable cream and mayonnaise available on the Brazilian market were analyzed for pyrene, chrysene, benzo(a)pyrene, benzo(b)fluoranthene and dibenzo(a,h)anthracene. The analytical methodology involved liquid-liquid extraction, clean-up on silica gel column and determination by high performance liquid chromatography using fluorescence detector. Variable levels of contamination were found within differents brands of the same product and within differents batches of the same brand. The total PAH content was in the range of 4.1 to 7.1mug/kg in vegetable cream, 1.7 to 3.9mug/kg in margarine and 1.0 to 21.7mug/kg in mayonnaise. In general the products which according to the label contain corn oil showed the highest levels of contamination. Based on these results and on the importance of fat, oils and derived products for the intake of PAHs, it is recommended that producers of margarine, vegetable creams and mayonnaise start to control the contamination of the vegetable oils used in the elaboration of these products, in order to reduce the exposure of consumers to excessive amounts of potentially carcinogenic compounds.

Metabolic activation of polycyclic aromatic hydrocarbons and other procarcinogens by cytochromes P450 1A1 and P4501B1 allelic variants and other human cytochromes P450 in Salmonella typhimurium NM2009

A variety of polycyclic aromatic hydrocarbons and their dihydrodiol derivatives, arylamines, heterocyclic amines, and nitroarenes, were incubated with cDNA-based recombinant (Escherichia coli or Trichoplusia ni) systems expressing different forms of human cytochrome P450 (P450 or CYP) and NADPH-P450 reductase using Salmonella typhimurium, tester strain NM2009, and the resultant DNA damage caused by the reactive metabolites was detected by measuring expression of umu gene in the cells. Recombinant (bacterial) CYP1A1 was slightly more active than any of four CYP1B1 allelic variants, CYP1B1*1, CYP1B1*2, CYP1B1*3, and CYP1B1*6, in catalyzing activation of chrysene-1,2-diol, benz[a]anthracene-trans-1,2-, 3,4-, 5,6-, and 8,9-diol, fluoranthene-2,3-diol, dibenzo[a]pyrene, benzo[c]phenanthrene, and dibenz[a,h]anthracene and several arylamines and heterocyclic amines, whereas CYP1A1 and CYP1B1 enzymes had essentially similar catalytic specificities toward other procarcinogens, such as (+)-, (-)-, and (+/-)-benzo[a]pyrene-7,8-diol, 5-methylchrysene-1,2-diol, 7,12-dimethylbenz[a]anthracene-3,4-diol, dibenzo[a,l]pyrene-11,12-diol, benzo[b]fluoranthene-9,10-diol, benzo[c]chrysene, 5,6-dimethylchrysene-1,2-diol, benzo[c]phenanthrene-3,4-diol, 7,12-dimethylbenz[a]anthracene, benzo[a]pyrene, 5-methylchrysene, and benz[a]anthracene. We also determined activation of these procarcinogens by recombinant (T. ni) human P450 enzymes in S. typhimurium NM2009. There were good correlations between activities of procarcinogen activation by CYP1A1 preparations expressed in E. coli and T. ni cells, although basal activities with three lots of CYP1B1 in T. ni cells were very high without substrates and NADPH in our assay system. Using 14 forms of human P450S (but not CYP1B1) (in T. ni cells), we found that CY1P1A2, 2C9, 3A4, and 2C19 catalyzed activation of several of polycyclic aromatic hydrocarbons at much slower rates than those catalyzed by CYP1A1 and that other enzymes, including CYP2A6, 2B6, 2C8, 2C18, 2D6, 2E1, 3A5, 3A7, and 4A11, were almost inactive in the activation of polycyclic aromatic hydrocarbons examined here.

Influence of tobacco smoke on carcinogenic PAH composition in indoor PM10 and PM2.5

Because of the mutagenic and/or carcinogenic properties, Polycyclic Aromatic Hydrocarbons (PAH), have a direct impact on human population. Consequently, there is a widespread interest in analysing and evaluating the exposure to PAH in different indoor environments, influenced by different emission sources. The information on indoor PAH is still limited, mainly in terms of PAH distribution in indoor particles of different sizes; thus, this study evaluated the influence of tobacco smoke on PM10 and PM2.5 characteristics, namely on their PAH compositions, with further aim to understand the negative impact of tobacco smoke on human health. Samples were collected at one site influenced by tobacco smoke and at one reference (non-smoking) site using low-volume samplers; the analyses of 17 PAH were performed by Microwave Assisted Extraction combined with Liquid Chromatography (MAE–LC). At the site influenced by tobacco smoke PM concentrations were higher 650% for PM10, and 720% for PM2.5. When influenced by smoking, 4 ring PAH (fluoranthene, pyrene, and chrysene) were the most abundant PAH, with concentrations 4600–21 000% and 5100–20 800% higher than at the reference site for PM10 and PM2.5, respectively, accounting for 49% of total PAH (SPAH). Higher molecular weight PAH (5–6 rings) reached concentrations 300–1300% and 140–1700% higher for PM10 and PM2.5, respectively, at the site influenced by tobacco smoke. Considering 9 carcinogenic PAH this increase was 780% and 760% in PM10 and PM2.5, respectively, indicating the strong potential risk for human health. As different composition profiles of PAH in indoor PM were obtained for reference and smoking sites, those 9 carcinogens represented at the reference site 84% and 86% of SPAH in PM10 and PM2.5, respectively, and at the smoking site 56% and 55% of SPAH in PM10 and PM2.5, respectively. All PAH (including the carcinogenic ones) were mainly present in fine particles, which corresponds to a strong risk for cardiopulmonary disease and lung cancer; thus, these conclusions are relevant for the development of strategies to protect public health.

Influence of traffic emissions on the carcinogenic polycyclic aromatic hydrocarbons in outdoor breathable particles

Because polycyclic aromatic hydrocarbons (PAHs) have been proven to be toxic, mutagenic, and/or carcinogenic, there is widespread interest in analyzing and evaluating exposure to PAHs in atmospheric environments influenced by different emission sources. Because traffic emissions are one of the biggest sources of fine particles, more information on carcinogenic PAHs associated with fine particles needs to be provided. Aiming to further understand the impact of traffic particulate matter (PM) on human health, this study evaluated the influence of traffic on PM10 (PM with aerodynamic diameter <10 µm) and PM2.5 (PM with aerodynamic diameter <2.5 µm), considering their concentrations and compositions in carcinogenic PAHs. Samples were collected at one site influenced by traffic emissions and at one reference site using lowvolume samplers. Analysis of PAHs was performed by microwave-assisted extraction combined with liquid chromatography (MAE-LC); 17 PAHs, including 9 carcinogenic ones, were quantified. At the site influenced by traffic emissions, PM10 and PM2.5 concentrations were, respectively, 380 and 390% higher than at the background site. When influenced by traffic emissions, the total concentration of nine carcinogenic compounds (naphthalene, chrysene, benzo(a)anthracene, benzo(b) fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene, and dibenzo(a,l)pyrene) was increased by 2400 and 3000% in PM10 and PM2.5, respectively; these nine carcinogenic compounds represented 68 and 74% of total PAHs (ƩPAHs) for PM10 and PM2.5, respectively. All PAHs, including the carcinogenic compounds, were mainly present in fine particles. Considering the strong influence of these fine particles on human health, these conclusions are relevant for the development of strategies to protect public health.

Polycyclic aromatic hydrocarbons in commercial squids from different geographical origins: levels and risks for human consumption

The concentrations of 18 polycyclic aromatic hydrocarbons (PAHs) were determined in five commercially valuable squid species from different geographical origins (Atlantic, Indic and Pacific Oceans). Out of the 18 quantified PAHs (the 16 PAHs considered by US EPA as priority pollutants, dibenzo(a,l)pyrene and benzo(j)fluoranthene) only dibenz(a,h)anthracene was not detected. The total concentrations of PAHs varied by a factor of more than 100-fold, from 0.22 (Loligo gahi) to 60.9 lg/kg ww (Loligo reynaudii). Intraand inter-specific variability of PAH levels was statistically assessed. Nine carcinogenic (probable/possible) PAHs accounted for 1% (L. reynaudii) to 26% (Loligo opalescens) of the total PAHs content being the main contributors naphthalene (in Loligo duvaucelii, L. reynaudii and Loligo vulgaris species), chrysene (in L. opalescens) and indeno(1,2,3-cd)pyrene (in L. gahi). PAHs source analysis indicated that four of the five zones of capture of the different squid species are significantly affected by both petrogenic and pyrolytic sources. Assessment of the target carcinogenic risks, established by the US EPA, suggested that L. gahi (Atlantic Ocean) and L. opalescens (from Pacific Ocean) may pose additional risks for consumers, if not eaten in moderation, derived from benzo(a)pyrene ingestion.

The use of forensic polycyclic aromatic hydrocarbon signatures and Compound Ratio Analysis Techniques (CORAT) for the source characterisation of petrogenic/pyrogenic environmental releases.

This study utilised recent developments in forensic aromatic hydrocarbon fingerprint analysis to characterise and identify specific biogenic, pyrogenic and petrogenic contamination. The fingerprinting and data interpretation techniques discussed include the recognition of: The distribution patterns of hydrocarbons (alkylated naphthalene, phenanthrene, dibenzothiophene, fluorene, chrysene and phenol isomers), • Analysis of “source-specific marker” compounds (individual saturated hydrocarbons, including n-alkanes (n-C5 through 0-C40) • Selected benzene, toluene, ethylbenzene and xylene isomers (BTEX), • The recalcitrant isoprenoids; pristane and phytane and • The determination of diagnostic ratios of specific petroleum / non-petroleum constituents, and the application of various statistical and numerical analysis tools. An unknown sample from the Irish Environmental Protection Agency (EPA) for origin characterisation was subjected to analysis by gas chromatography utilising both flame ionisation and mass spectral detection techniques in comparison to known reference materials. The percentage of the individual Polycyclic Aromatic Hydrocarbons (PAIIs) and biomarker concentrations in the unknown sample were normalised to the sum of the analytes and the results were compared with the corresponding results with a range of reference materials. In addition, to the determination of conventional diagnostic PAH and biomarker ratios, a number of “source-specific markers” isomeric PAHs within the same alkylation levels were determined, and their relative abundance ratios were computed in order to definitively identify and differentiate the various sources. Statistical logarithmic star plots were generated from both sets of data to give a pictorial representation of the comparison between the unknown sample and reference products. The study successfully characterised the unknown sample as being contaminated with a “coal tar” and clearly demonstrates the future role of compound ratio analysis (CORAT) in the identification of possible source contaminants.

Fotodegradação de hidrocarbonetos policíclicos aromáticos em placas de sílica impregnadas com dióxido de titânio

Photodegradation of the PAHs anthracene, chrysene and benzo[k]fluoranthane on silica gel impregnated with TiO2 and over glass plates holding TiO2 was studied. Silica gel plates holding these substances were exposed to solar radiation, developed with hexane and photographed under ultra-violet light. The plates containing benzo[k]fluoranthene were also analysed by both diffuse reflectance and laser induced fluorescence. Diffuse reflectance spectra of the fluorescent spot from non irradiated plates showed small differences when compared with those obtained from irradiated plates. These spectral differences are compatible with formation of less conjugated compounds during irradiation. Fluorescence and time resolved fluorescence spectra observed after irradiation were identical to those obtained with benzo[k]fluoranthene in methanol. On plates holding silica, PAH degradation requires longer periods of solar irradiation when compared with those plates containing silica impregnated with TiO2. Glass plates impregnated with TiO2 also showed very rapid PAH degradation.

Investigations on the Effects of Petroleum Hydrocarbons on the Marine Bivalves Perna viridis (Linnaeus) and Sunetta scripta (Linne')

The thesis deals with different aspects connected with the distribution and toxicity of PHC in crude oils in the aquatic environment and marine molluscs. Information has been gathered and presented on the present status of research in the field based on a thorough review of recent literature. It is seen from the literature that the resident time of PHC becomes lesser and lesser when crude oil is discharged in large quantities into the coastal waters where excess oxygenation light penetration, temperature availability and strong tidal currents persist. This results in the reduction of the onslaught of oil pollution. This probably shows that taxic insult of crude oil in tropical shores will be relatively lesser than that occurring in temperate and boreal waters. However, there is no record of major episodal oil pollution comparable in quantum and extent to that of Torrey Canyon or Amoco Cadiz which prevents a more reliable analysis on the issue. Considerable controversy exists on the method of estimation of PHC in seawater. However, Ultra-violet fluorescence spectroscopy has been widely recommended as an analytical tool for the determination of total hydrocarbons. Similarly representation of values as chrysene equivalents has been recognised as the most reliable method of Quantum representation.

Bile metabolites of polycyclic aromatic hydrocarbons (PAHs) in European eels Anguilla anguilla from United Kingdom estuaries

A total of 94 European eels (Anguilla anguilla) were collected from five estuaries in the UK. The deconjugated metabolites of polycyclic aromatic hydrocarbons (PAHs) in the bile of the eels were separated using HPLC. Six PAH metabolites were identified: 1-hydroxy (1-OH) metabolites of phenanthrene, pyrene and chrysene; and the 1-OH, 3-OH and 7,8 dihydrodiol metabolites of benzo[a]pyrene (BaP). The mean concentration of the six metabolites was greatest in eels from the Tyne (49 muM) followed by the Wear (33 muM), Tees (19 muM), Thames (4 muM) and Severn (2 muM) estuaries. Although 1-OH pyrene was always the dominant compound, there were significant differences (P<0.05) between sites and between estuaries for some metabolites. Normalising the molar concentration of the bile metabolites to the bile biliverdin absorbance reduced sample variation. When the metabolites identified were-each expressed as a percentage of the total detected, the metabolite profile was characteristic for each estuary. (C) 2002 Elsevier Science B.V. All rights reserved.

Tratamento eletroquímico de água produzida sintética para remoção de hidrocarbonetos policíclicos aromáticos

The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive

Hidrocarbonetos policíclicos aromáticos em sedimentos e organismos bentônicos do Terminal de Miramar (Baía do Guajará - Belém - Pará - Amazônia)

ABSTRACT: In Guajará bay, mouth of the Amazon River, is located the capital of Pará state (Belém) and its metropolitan area. Exists in this area an intense boat traffic, as well as transportation and sale of fuels in floating docks and activities related to the storage and transportation of oil in Miramar Petrochemical Terminal (TEMIR). Small spills and discharges of oil in water can serve as sources of pollution by polycyclic aromatic hydrocarbons (PAHs). PAHs are organic compounds generated by incomplete combustion of organic matter (OM) and are among the contaminants of most interest in environmental studies due to their mutagenic and carcinogenic potential. One way to detect and evaluate the impact of PAHs in an environment is using biomonitors, however the qualitative and quantitative analysis in sediments are most widely used. This study aimed to evaluate, by Gas Chromatography/Mass Spectrometry (GC/MS), the 16 PAHs considered as priority by the Environmental Protection Agency of the United States in sediments and benthic organisms (Namalicastys abiuma) of TEMIR. Field expeditions were carried out in December 2012, March, May and June 2013 representing the dried, wet (two samples) and dried seasons successively. Fine sediments levels dominated in both sampling periods and the %Fines in Guajará bays has a direct relationship to the %OM. In relation to the 16 PAHs studied, 10 of them were detected in the wet season sediments samples and 8 in the dried season. Even with a low diversity of aromatic compounds, sediment samples of the dried season presented greater ΣHPAs (1.351,43 ng g^-1) than the sediments of the wet season (263,99 ng g^-1), which can be related to the increased hydrodynamic in Guajará bay this last period. Correlation analysis indicated that ΣHPAs not seem to be influenced by %Fine and %OM. Benzo(a)pyrene accounted for 87% of ΣHPAs during the wet season, the other PAHs showed percentage ≤ 3%. During the other period stood out: pyrene (18% of ΣHPAs) fluoranthene (16%), the chrysene, benzo(b)fluoranthene (15%) and benzo(a)pyrene (11%). The use of the geochemical reason to interpret likely sources of PAHs indicated that there is a predominance of aromatics from pyrolytic origin in TEMIR. The activities that may be responsible for the PAHs levels observed in sediments and benthic organisms in TEMIR are the discharge of untreated domestic sewage and the emissions of particulates from cars and small/medium boats. The ΣHPAs seems to influence the density of polychaetes because a reduction of about 50% in the number of organisms was observed during the dry season when there was the greater amount of ΣHPAs in their body structure. Among the 16 PAHs studied, 11 were detected in the polychaetes during the dry season (ΣHPAs_MED = 848,71 ng g^-1) and 10 in the wet season (ΣHPAs_MED = 141,85 ng g^-1). Were highlighted during the dried season: indeno(1,2,3-c,d)pyrene (47%) and pyrene (23%). While in the wet season: pyrene (23%), chrysene (17%), fluorene (17%) and fluoranthene (13%). The %Rec obtained was >>100% indicating a matrix effect and reducing the quantitative accuracy of results. The use of the polychaete N. abiuma as biomonitor of pollution by PAHs in estuaries not seem to be effective when the sample period is limited, because collecting it requires a great effort to obtain a small amount of mass and it still results in a matrix effect in the chromatographic analysis (method %Rec >> 100%) that may not be corrected due to the restricted availability of sample mass. Studies with a larger number of samples, enabling depth statistical analysis, and covering other collection points in Guajará bay are required to prove mathematically that has been stated in this dissertation.