De l'IR au submillimétrique, le spectre du milieu interstellaire (MIS) est dominé par l'émission des grains de poussière interstellaires. Les plus petits d'entre eux, les PAHs, sont en fait de grosses molécules aromatiques polycycliques hydrogénées. Leur présence est attestée par l'observation d'une série de bandes vibrationnelles dans l'IR moyen, caractéristiques de modes de vibration C-C et C-H sur des cycles aromatiques. Etant donnée l'importance des PAHs pour la physique et la chimie du MIS (chauffage du gaz, formation de H2), il est essentiel de trouver d'autres observables pour contraindre leurs propriétés. L'émission micro-onde des grains interstellaires qui sera observée prochainement avec le satellite Planck est de ce point de vue une opportunité. En effet, les efforts faits récemment dans le but de mesurer les fluctuations du fonds diffus cosmologique ont motivé une étude détaillée des émissions Galactiques dans le domaine micro-onde. Un excès d'émission inattendu a été découvert entre 10 et 90 GHz et ne peut être expliqué par aucun des mécanismes d'émission déjà connu dans ce domaine de fréquences. Cet excès, baptisé « émission anormale », s'est révélé être corrélé à l'émission IR des grains interstellaires. L'origine de l'émission anormale pourrait être l'émission dipolaire électrique de PAHs en rotation.<br /> L'objectif central de ma thèse est la compréhension de l'émission des PAHs interstellaires à grande longueur d'onde en vue de mieux contraindre leurs propriétés et de préparer l'analyse des données Planck-Herschel. Mon travail de thèse a consisté en deux parties complémentaires : modélisation de l'émission des PAHs interstellaires de l'IR proche au centimètre, puis confrontation de ce modèle aux observations disponibles dans le but d'obtenir un modèle physique.<br /> La première partie de mon travail de modélisation concerne l'émission rovibrationnelle des PAHs. J'ai adopté une section efficace déduite des observations ISO et Spitzer pour λ ≤ 20 µm. A plus grande longueur d'onde, trois modes vibrationnels ont été ajouté à partir des travaux théoriques de Malloci et al. (2007). Ce modèle permet de reproduire le spectre du milieu diffus et d'une région de photodissociation avec un mélange de PAHs neutres et ionisés. J'ai par ailleurs montré que si l'émission rovibrationnelle des PAHs dans l'IR moyen est proportionnelle à l'intensité du champ de rayonnement, ce n'est plus le cas pour λ ≥ 3 mm. La seconde partie a consisté en la modélisation de l'émission purement rotationnelle des PAHs. J'ai utilisé des propriétés moléculaires réalistes et traité les interactions avec les atomes et les ions du gaz interstellaire. L'excitation et le freinage par émission de photons rotationnels et rovibrationnels ont également été inclus. L'émission rotationnelle en bande large a été estimée pour une large gamme de conditions astrophysiques et de propriétés des grains. J'ai par ailleurs mis en évidence l'indépendance du spectre d'émission rotationnelle par rapport à l'intensité du champ de rayonnement G0 et à la densité du milieu dans lequel les grains se trouvent nH (G0 ≤ 100 et nH ≤ 30 cm-3).<br /> J'ai ensuite confronté les résultats de cette modélisation aux observations disponibles. La première étape a été l'extraction de l'émission anormale des données WMAP, à laquelle j'ai participé. Nous avons pu mettre en évidence l'existence d'une composante anormale forte, non polarisée, à 23 GHz. Elle a été incluse dans le Planck Sky Model. Pour la première fois, nous avons pu montrer que l'émission anormale est bien corrélée avec l'émission des poussières et que cette corrélation est meilleure à 12 µm (caractéristique des PAHs) qu'à 100 µm (caractéristique de grains plus gros). J'ai également montré l'indépendance de l'émission anormale par rapport à l'intensité du champ de rayonnement, une des prédictions du modèle. Les caractéristiques des grains déduites de l'émission anormale sont par ailleurs en accord avec celles déduites de l'émission IR. J'ai également étudié la région moléculaire G159.6-18.5 dans Persée et montré que son spectre d'émission anormale est bien ajusté avec une distribution de tailles bimodale, en accord avec les travaux théoriques de Le Page et al. (2003).

Induction of the cytochrome P450(CYP)1A protein and the connected increase in 7-ethoxyresorufin O-deethylase (EROD) activity are common biomarkers in fish. Enhanced activity of this protein signals exposure to Ah-receptor agonists such as chlorinated dioxins, co-planar polychlorinated biphenyls (PCBs) and certain polycyclic aromatic hydrocarbons (PAHs). The EROD biomarker is commonly analyzed in liver microsomes. However, the gill is directly exposed to waterborne pollutants, and in this thesis the gill filament EROD assay was therefore evaluated as a monitoring tool for waterborne CYP1A inducers in fish. Originally developed in rainbow trout (Oncorhynchus mykiss), the assay was here applied in various limnic and marine species. Following exposure to low waterborne concentrations of the readily metabolized CYP1A inducers benzo(a)pyrene (BaP) and indigo, a strong EROD induction was observed in the gill but not in the liver. This likely reflected metabolic clearance of the inducers in gill and other extrahepatic tissues. The high sensitivity of the gill was confirmed in studies of fish caged in waters in urban and rural areas in Sweden where the gill consistently showed a more pronounced EROD induction compared with the liver and the kidney. Fish caged in the reference waters showed surprisingly strong gill EROD induction and CYP1A immunostaining. Consequently, there may be CYP1A inducers present in the aquatic environment that are not yet identified. The assay was further applied in Atlantic cod (Gadus morhua) as a biomarker of exposure to crude oil and produced water (PW) from oil fields in the North Sea. The assay was finally adapted to detect inhibiting compounds, and an imidazole, a triazole and a plant flavonoid turned out to be potent gill EROD inhibitors. The overall conclusion from the studies of this thesis is that the gill filament EROD assay is a practical and sensitive biomarker of exposure to waterborne CYP1A inducers in various fish species. The induction of gill EROD activity in fish also at the reference sites in the field studies calls for further studies on background contamination in Swedish waters.

Soot and other products of incomplete combustion play an important role in the chemistry of the atmosphere. As particles are exposed to trace gases, such as ozone, their chemistry and physical properties can be altered leading to changes in their optical properties, as well as their cloud condensation nuclei and ice nucleation abilities. These alterations can lead to changes in the global radiative budget and cloud microphysical processes, which in turn affect the climate. In this study, the chemical and physical changes associated with the oxidation of pyrene, anthracene, and carbon (lampblack) by ozone were investigated. Fourier Transform Infrared Spectroscopy was used to identify oxidation products and track reaction progress for these representative aerosols. A C=O band attributed to a carboxylic acid formation was observed for all three substances, at each level of exposure to ozone - 20 ppm, 40 ppm, and 80 ppm. Second order reaction rate constants ranged from 9.58 x 10-16 cm2 molecules-1 s-1 to 7.71 x 10-13 cm2 molecules-1 s-1. Measurements of water uptake, ice nucleation efficiency, and optical properties were obtained to determine whether any physical changes associated with the oxidation process occurred. Optical measurements show an increase in the ultra-violet absorption of anthracene, but not for pyrene, while an increase in the visible absorption for pyrene was observed, but not for anthracene. Oxidized soot froze at a warmer temperature (-22.8 degrees C) then fresh soot (-25.6 degrees C), showing an increase in ice nucleation efficiency. Our data indicates that oxidation by ozone does alter the chemistry and physical properties of the substances study, leading to possible changes in how they interact with atmospheric processes.

Ma thèse est dédiée aux propriétés et à l'évolution des poussières dans le milieu interstellaire (MIS) Galactique et en particulier aux plus petites tailles de la distribution des grains. Tout au long de ces trois années, de nouvelles observations infrarouges (IR) du télescope spatial Spitzer m'ont permis d'apporter ma propre contribution à la connaissance du cycle de vie des poussières. Afin d'en acquérir une vision la plus globale possible, j'ai étudié trois types d'environnements interstellaires différents : le milieu diffus Galactique, un nuage moléculaire et une région de formation d'étoiles.<br />J'ai analysé une ligne de visée qui pointe en direction du MIS diffus Galactique, en évitant les régions brillantes de formation d'étoiles. En combinant des données spectroscopiques et photométriques, j'ai construit un spectre Galactique moyen de l'émission de la poussière dans le proche et moyen IR, qui m'a ensuite servi de référence. Les bandes des hydrocarbures aromatiques polycycliques (HAPs) sont visibles ainsi qu'un continuum. Afin d'interpréter les rapports<br />d'intensité des bandes en termes de taille et d'état d'ionisation des HAPs, j'ai mis à jour notre modèle de poussières, de telle sorte qu'il tienne compte de la dépendance de l'état d'ionisation des HAPs en fonction de leur taille. Le spectre du MIS diffus est ajusté pour une taille moyenne des HAPs de 60 atomes de carbone et pour une fraction de cation de 40%. Des HAPs de taille moléculaire et chargés sont donc présents dans le milieu diffus. Un continuum vers 3-5 μm, originellement détecté dans des nébuleuses par réflexion, est également présent dans l'émission du MIS diffus. Ce continuum explique 70% de l'émission dans le filtre Spitzer/IRAC à 3.6 μm. Son origine demeure inconnue. Je montre qu'il ne s'agit ni de lumière diffusée ni de fluorescence des HAPs puisque ce processus requiert une efficacité de conversion des photons supérieure à 100%.<br />J'ai utilisé les observations Spitzer pour quantifier les variations spatiales des propriétés des HAPs à travers la Galaxie et sur de petites échelles dans le nuage moléculaire du Taureau. L'analyse d'un échantillon de lignes de visée du MIS diffus Galactique montre que la taille moyenne des HAPs varie de manière signiffcative, de 40 à 80 atomes de carbone, tandis que leur fraction d'ionisation demeure constante dans les barres d'erreur. J'ai également analysé les images Spitzer du nuage moléculaire du Taureau dans l'IR moyen et lointain. Chaque composante de poussières (HAPs, TPGs pour Très Petits Grains et GGs pour Gros Grains) peut être associée à un canal Spitzer (IRAC 8, MIPS 24 et MIPS 160 μm). Une première difficulté était d'obtenir les images de l'émission diffuse de faible brillance pour le nuage complet. J'ai travaillé avec les spécialistes du Centre Spatial Spitzer (CSS) afin de produire les images IRAC 8 μm et MIPS 24 μm. Pour MIPS 160 μm, j'ai utilisé un algorithme d'inversion développé pour supprimer certains effets instrumentaux des données. J'ai validé la photométrie de ces images. Les observations montrent que les HAPs sont seulement présents au sein d'une couche en surface plus fine que celle pénétrée par les photons ultraviolets et que celle où émettent les TPGs. Ces variations ne peuvent être expliquées par un simple effet d'extinction et révèlent une réelle disparition des HAPs dans le gaz dense où les plus petites particules pourraient se coller sur les plus gros grains et/ou coaguler.<br />Pendant ma thèse, j'ai postulé à une bourse du CSS dans le but d'étudier la Nébuleuse de l'Aigle (M16), l'objet céleste qui m'a décidé à faire de l'astrophysique, il y a plus de dix ans, lorsque le télescope spatial Hubble a photographié les fameux Piliers de la Création. Ma candidature a été acceptée et j'ai passé six mois au sein de l'équipe scientifique MIPSGAL. Mon objectif était de combiner les données IRAC et MIPS de M16 afin d'analyser les propriétés des grains dans les structures de gaz et de poussières, tout en m'impliquant dans le traitement des données. L'image MIPS à 24 μm révèle une structure en forme de coquille à l'intérieur de la nébuleuse tandis que les piliers sont visibles aux autres longueurs d'onde. M16 est une région de formation d'étoiles massives où l'émission de la poussière est censée être alimentée par le rayonnement des étoiles massives. Cependant, nous montrons que le champ de rayonnement ultraviolet est un ordre de grandeur plus faible que celui requis pour expliquer la température de la poussière dans la coquille. À des fins comparatives, nous avons également analysé plusieurs autres coquilles Galactiques. La Nébuleuse de l'Aigle est particulière dans le sens où elle possède une température de couleur IR lointain inhabituellement élevée. Nous avons envisagé une interprétation selon laquelle la poussière est chauffée par les collisions avec le gaz. Cette interprétation implique que la coquille est un reste de supernova (RSN) d'environ 3000 ans. Si cela était confirmé, le RSN de l'Aigle serait le premier détecté grâce à l'émission de la poussière et au sein d'une pouponnière stellaire. De plus, cela illustrerait l'importance de l'émission infrarouge de la poussière dans l'étude énergétique des RSNs. Dernier point, et non des moindres, la question de la formation et/ou destruction des fameux Piliers de la Creation serait (ré)ouverte.

Exposure to crude oils has been shown to induce CYP1A enzymes and cause chronically toxic effects in aquatic organisms. Earlier studies indicated that polycyclic aromatic hydrocarbons (PAHs) present in crude oil are primarily responsible for the chronic toxicity. Crude oil contains a variety of PAHs; the majority of them are alkyl substituted. In this work, we have used an effects-driven fractionation and analysis approach (EDFA) to isolate and characterize PAHs present in Alaskan North Slope and Scotian Light crude oils that are toxic to fish. The crude oil components were first fractionated into four fractions using a low temperature vacuum distillation technique. Among them, the heavy gas oil fraction (boiling range 287°C – 461°C) of both oils caused highest toxicity to fish. To isolate the PAHs from waxes present in this fraction, a low temperature wax precipitation method was developed and optimized. CYP1A induction results showed that the extract contained a large number of CYP1A inducers while the residue contained none. Chemical analyses confirmed that most of the PAHs were partitioned into the extract fraction. Alkyl PAHs present in the extract were further fractionated into five fractions based on the number of aromatic rings using a normal phase HPLC method. Chemical analysis and the toxicity testing of these fractions indicated that alkyl PAHs belonging to classes such as phenanthrene, fluorene, naphthobenzothiophene, and chrysene are likely responsible for the observed toxic effects. To aid the EDFA scheme, a new HPLC-DAD method for the analysis of alkyl PAHs was developed. The alkyl PAHs were first fractionated based on the number of aromatic rings using a normal phase column followed by their analysis using reverse phase HPLC–DAD technique. The reverse phase analysis involved classifying the alkyl PAH peaks into different PAH classes based on their DAD spectra. Then, alkyl carbon numbers for each peak were assigned based on their retention time. To analyze co-eluting alkyl PAH isomers an offline multi-dimensional HPLC method was developed. Orthogonal separation was achieved by first fractionating the alkyl PAHs on a normal phase column followed by the RP-HPLC-DAD analysis. Using these data a 2D contour plot was developed and used for the detailed analysis of alkyl PAHs isomers. Analysis results showed good agreement with a gas-chromatography-mass-spectrometric (GC-MS) analysis method, and the new method was able to distinguish some PAH types which could not be identified by GC-MS. / Thesis (Ph.D, Chemistry) -- Queen's University, 2007-11-19 13:46:18.602

The remediation of soil contaminated with polycyclic aromatic hydrocarbons (PAHs) is endorsed by environmental protection agencies worldwide. Recent studies demonstrated the removal of these contaminants from soil utilizing polymer beads, with subsequent PAH release and degradation in solid-liquid two phase partitioning bioreactors (TPPBs). Although such a process was successful, significant mass transport limitations involving PAH release from the polymers hampered productivity. The current work examined the possibility of applying sonication in solid-liquid partitioning systems to enhance delivery and degradation of PAHs. Small scale physical testing revealed delivery rates of PAHs from Desmopan, increased by 5 fold under intermittent sonication relative to non-sonicated conditions. Enhancements were also displayed as shifts to higher release equilibria under sonicated conditions, agreeing with sonochemistry concepts. Improvements were demonstrated across a range of polymers, suggesting that sonication could enhance PAH release with any polymers deemed feasible for environmental applications. A PAH-degrading microbial consortium was enriched, and it was demonstrated that sonication also improved the rate of phenanthrene degradation delivered from Desmopan by four times, confirming transport improvements while minimizing cellular inactivation effects. A mass transport analysis showed that without sonication, delivery of PAHs was restricted by the external resistance at the solid-liquid interface. Ultrasound was shown to enhance both external and internal transport properties, allowing rates not achievable through increased liquid mixing. Diffusivities quantified with and without ultrasound decreased as a function of permeant molecular size. Additionally, partitioning coefficients under sonicated and non-sonicated conditions decreased with PAH molecular size. Finally, an examination of permeant property data demonstrated that polarizability was the best descriptor of thermodynamic and transport behaviour in solid-liquid systems. The possibility of inducing equivalent improvements was investigated in a bench scale TPPB, in which sonic exposure improved degradation rates of phenanthrene by 2.7 fold when delivered from Desmopan. A window of on/off operation for ultrasonic cycling was also demonstrated, providing potential for optimizing sonication via rational selection of exposure times. DNA analysis also revealed that the consortium composition was maintained in the presence of sonication and also demonstrated that the consortium was comprised of bacteria belonging to the Pandoraea, Sphingobium, and Pseudoxanthomonas genera. / Thesis (Master, Chemical Engineering) -- Queen's University, 2009-08-26 13:04:26.229

The induction of hepatic cytochrome P4501A1 and its monooxygenase activity 7-ethoxyresorufin O- deethylase, (EROD) in fish by PAHs, PCBs and dioxins has been suggested as an early warning system &ldquo / most sensitive biochemical response&rdquo / for assessing environmental contamination conditions. In this study, the degree of induction of cytochrome P4501A1 protein as determined immunochemically and CYP1A1 associated EROD activity in fish were utilized as biomarkers of exposure to PAHs, PCBs and related organic pollutants along the izmir Bay on the Aegean Sea Coast after the Great Canal Project. Three different fish species were used throughout this study, namely leaping mullet (Liza saliens), annular seabream (Diplodus annularis) and common sole (Solea vulgaris) which were representatives of pelagic, benthopelagic and benthic fish, respectively. Fish were sampled in November 2002 and October 2003 from different sites of the Bay. The mullet caught from Harbor, &Uuml / &ccedil / kuyular port site, and Pasaport region displayed highly elevated EROD activities which were 2258&plusmn / 840 (n=15), 2011&plusmn / 490 (n=4), 1813&plusmn / 287 (n=11) pmole /min/mg protein, respectively and were 104, 80 and 79 fold higher than that of fish obtained from the reference point (25&plusmn / 9 pmole/min/mg protein / n=4). Mullet caught along the pollutant gradient at three other sites (Hekim Island, inciralti, and Zeytinalani) exhibited less but highly significant induced EROD activity. EROD activities of common sole sampled from Fo&ccedil / a open sites (107&plusmn / 20 pmol/min/mg protein, n=5) and site16A (80&plusmn / 12 pmol/min/mg protein, n=9) were found to be very low and the latter was accepted as reference site. The highest EROD activity were seen in fish captured from inciralti which was about 6.3 times higher than those obtained from reference site. Common sole caught from the mouth of Gediz River and Hekim Island exhibited also highly elevated EROD activities. Annular seabream was tested to monitor CYP1A inducing chemicals for the first time in this study. The highest EROD activity (1376&plusmn / 279 pmol/min/mg protein, n=8) were detected in fish samples collected from Harbor region. An inverse relationship was found between distance to the harbor region and EROD activities of annular seabream captured from other sampling sites. In this study for the first time, major cytochrome P450 dependent mixed function oxidase activities such as benzphetamine N- demethylase, ethylmorphine N-demethylase and aniline 4- hydroxylase, were characterized in annular seabream. Changes in the P450 1A1 protein level were determined by immunochemical analysis to monitor the pollutant based induction in all fish species and good correlation was obtained between EROD activity and CYP1A protein content. Fish from polluted sites had both highly induced EROD activity and cytochrome P450 1A content. Chemical analysis of total PAH concentration in sediment and liver tissues of some fish sample were also carried out. Although, izmir Great Canal Project has been active since 2000 to treat and protect the izmir Bay from the contamination of domestic and industrial wastes this study clearly demonstrated that the level of PAH, PCB and dioxin type persistent organic contaminants are still very high especially in the Inner and Middle Bay. This has implications for human fish consumption from contaminated areas, as well as for the health status of aquatic organisms.

In this work, wet deposition samples were collected at Middle East Technical University campus, Ankara, between December 2000 and May 2002. Snow samples were collected from 50 grids in January, 2001 in Ankara to investigate dry deposition of PAHs. The collected samples were preconcentrated by Solid Phase Extraction and ultrasonic extraction tecniques. Extraction methodologies were improved prior to analysis of samples. Extracted samples were analyzed by Gas Chromotography-Mass Spectrometry for 14 Polycyclic Aromatic Hydrocarbons. Selected Ion Monitoring mode was used throughout the analysis. Phenanthrene, fluoranthene, pyrene and benzo (b+k) fluoranthene were found to be dominant PAHs in wet deposition samples. Seasonal variation of PAHs were observed having higher concentrations in winter period. Meterological parameters were also examined together with PAH concentrations. Contribution of PAHs coming from North East and South West direction were found to be dominant. Wet deposition fluxes were calculated and compared with other urban sites. Wet deposition fluxes are lower than industrial sites and comparable with urban sites in Europe. PAH ratios and factor analysis results demostrated combustion and traffic emissions are major sources of pollutants in the city. Dry deposition of PAHs were invesigated using snow as a natural collecting surface. Dry deposition fluxes calculated using snow surface are compareble with other similar sites. Dry deposition pollution maps of PAHs were drawn by MapInfo software and it was observed that the major pollution regions are the localities where low income families live and low quality coal used for heating purpose. Ratio calculations showed that the central parts of the city is mostly affected from traffic emissions while coal emissions are dominating at the other parts of the city. Factor analysis applied to data set and 6 factors distinquished as coal, soil, traffic, oil combustion, mixed combustion and road dust.

Polycyclic aromatic hydrocarbons (PAHs) are a group of toxic air pollutants formed during incomplete combustion and are ubiquitously distributed in the environment. To determine particle-bound PAHs in archived PM2.5 samples taken with low flow rate in Atlanta, a sensitive and robust method was developed for measuring 28 PAHs and methyl PAHs in PM samples using isotope dilution gas chromatography/high resolution mass spectrometry (GC/HRMS). The method was then used to analyze PM2.5 samples collected at three sites (rural, urban, suburban-highway) from the Assessment of Spatial Aerosol Composition in Atlanta (ASACA) network. Distinct seasonal and spatial variations were observed in PAH concentration. Particle-bound PAH levels were significantly higher in winter than in summer. The suburban-highway site had higher PM2.5-bound PAH concentration than did the urban site, and the rural site had the lowest PAH levels. Retene, a proposed biomass burning tracer, captured both the high leaves-grasses-bushes-branches burning season and the high wood burning months, suggesting that it might be a better marker for all biomass burning, while potassium ion might be a more specific tracer for wood burning. Human exposure to PAHs can be assessed by characterizing their hydroxy PAH (OH-PAH) metabolites in urine samples. A method was developed to measure 24 urinary OH-PAHs, metabolites of 8 parent PAHs, using enzymatic de-conjugation, automatic liquid-liquid extraction, and GC/HRMS. A study was then carried out to evaluating the variability of the urinary biomarker levels in a non-occupationally exposed non-smoking reference group. Levels of urinary PAH metabolites varied widely both within-subject and between-subjects and the within-day variance far exceeded the between-day variance. There were also considerable temporal correlations for these biomarkers. Sample size calculations were conducted and taking 24-hour voids would require the least number of subjects, which should be considered during epidemiological study design. Finally, a study was conducted to evaluate exposure to ambient PAHs in an urban setting among 8 non-occupationally exposed non-smoking volunteers employing both personal air sampling and urine biomonitoring. PAH levels varied largely in air samples taken at home, at work, and while driving or jogging. Monitoring urinary OH-PAH levels can capture both inhalation and dietary exposures. Total inhaled PAH was correlated with total excreted OH-PAHs, suggesting that by combining personal air sampling and biomonitoring, exposure to environmental PAHs can be well characterized even for low-level exposure.

Os hidrocarbonetos policíclicos aromáticos (HPA) são amplamente estudados na área de meio ambiente, em diversas matrizes ambientais como ar, água, solo e sedimento, devido a sua toxicidade, potencial mutagênico e carcinogênico. Por conta disto, as agências ambientais de países desenvolvidos listaram dezesseis HPA como sendo poluentes prioritários. As legislações a nível mundial não estipulam limites para estes compostos para ar ambiente, somente para emissões de fontes fixas e móveis e ambientes ocupacionais, mas existem diversos estudos, mais especificamente para os 16 prioritários HPA e muito pouco para os homólogos alquilados. Os HPA alquilados são mais abundantes, persistentes e frequentemente mais tóxicos que os não alquilados e a toxicidade aumenta com o número de substituições alquil sobre os núcleos aromáticos. As legislações ambientais em todo o mundo não realizam o controle em nenhuma matriz ambiental para os HPA alquilados. Neste trabalho foi desenvolvido um método para análise dos HPA e seus homólogos alquilados, utilizando cromatografia de fase gasosa acoplado a um detector de espectrometria de massa e com um sistema de injeção para grande volume, associado à vaporização com temperatura programada, que permitiu um nível de detecção na faixa de 0,70 até 103,6 ng mL-1, sendo possível analisar as amostras de material particulado oriundas de emissões veiculares. As amostras foram coletadas de acordo com a Norma ABNT NBR14489, em um dinamômetro de bancada para motor do ciclo diesel (Ciclo de 13 pontos). Os resultados encontrados foram na faixa de 0,5 ng mL-1 até 96,9 ng mL-1 Os resultados indicaram que motores a diesel/ biodiesel têm uma contribuição muito grande na formação destes HPA e homólogos alquilados