971 resultados para Off-line TMAH-GC-MS
Resumo:
FUNDAMENTO: Embora as doenças cardiovasculares sejam a maior causa de morbimortalidade em todo Brasil, o acesso das populações de cidades pequenas à eletrocardiografia e à avaliação cardiológica é limitado. O uso da telecardiologia para facilitar o acesso da população de municípios remotos à eletrocardiografia e à segunda opinião em cardiologia é promissora, entretanto não foi formalmente testada. OBJETIVO: Avaliar a viabilidade de se implantar o sistema público de telecardiologia de baixo custo em pequenas cidades brasileiras. MÉTODOS: Foram selecionadas 82 cidades do Estado de Minas Gerais, com população < 10.500 habitantes, > 70% de cobertura pelo Programa Saúde da Família (PSF), com interesse do gestor e acesso pela internet. Em cada município foi instalado um aparelho de eletrocardiógrafo (ECG) digital, com subsequente treinamento da equipe. A implantação foi coordenada pelo HC/UFMG, em conjunto com outros quatro hospitais universitários mineiros (UFU, UFTM, UFJF e UNIMONTES). Os ECGs foram realizados nos municípios e enviados pela internet para análise imediata em plantão de telecardiologia. Realizaram-se discussões de casos médicos on-line e off-line e cursos de atualização via web. RESULTADOS: No período de implantação, foram treinados 253 profissionais de saúde. De julho de 2006 a novembro de 2008, o projeto atendeu 42.664 pacientes, realizando 62.865 ECGs. Foram efetuados 2.148 atendimentos de urgência e 420 teleconsultorias. A avaliação intermediária apontou boa aceitação da tecnologia implantada e uma diminuição de 70% de encaminhamentos de pacientes para outros centros de referência. CONCLUSÃO: É factível a utilização de recursos habituais de informática para facilitar o acesso de populações de cidades pequenas à eletrocardiografia e avaliação cardiológica especializada.
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El análisis de ácidos grasos es de gran interés para la industria cárnica por las implicaciones tecnológicas, nutricionales y sensoriales que se derivan de su composición (Nicolau y Kokotos, 2004; Sédébio y Christie, 1998; Livisay et al. 2000). Además se han estudiando de forma muy intensa la influencia del sexo, raza, peso y alimentación en la composición y distribución de los ácidos grasos tanto en el tejido muscular como en el subcutáneo (De Smet et al. 2004). La tendencia a modificar la composición de los ácidos grasos a través de la dieta ha motivado la necesidad de métodos de análisis más precisos y exactos para poder determinar la concentración de ácidos grasos, como por ejemplo algunos del tipo n-3: linolénico, eicosapentaenoico (EPA) y docosahexaenoico (DHA); y otros que han adquirido importancia tanto por sus propiedades en producción animal como por su efecto sobre la salud humana, como el CLA y los ácidos grasos trans. La separación de los isómeros del CLA es un análisis muy complejo y fundamental para poder calcular las concentraciones de los isómeros más activos (Winkler y Steinhart, 2001); esta dificultad se puede extender a los ácidos grasos trans de los ácidos grasos oleico, linoleico y linolénico. La forma más extendida de cálculo de la composición de ácidos grasos es la de los porcentajes normalizados. Sin embargo, cada vez es más importante el cálculo de las concentraciones de ácidos grasos lo que requiere la validación del método de modo más complejo. Los diferentes métodos de extracción pueden producir concentraciones diferentes, por ello es un aspecto a considerar como previo. El método de extracción más extendido, sin considerar el método oficial para la determinación de grasa total, es el descrito por Folch et al. 1957. Este método ha sido modificado con variantes pero que mantienen el mismo principio de extracción basado en la mezcla de cloroformo y metanol para poder extraer tanto lípidos neutros como polares. Dado el uso de cloroformo se han propuesto otras soluciones de extracción como el hexano:2- propanol, pero que no han sido aplicadas de modo importante. Una vez extraídos los lípidos se han de saponificar para liberar los ácidos grasos y a continuación formar los ésteres metílicos que se separaran mediante cromatografía de gases. Para producir los ésteres metílicos de los ácidos grasos existen varios métodos que ofrecen resultados comparables pero no completamente similares. Por lo cual este es otro elemento a considerar, sobre todo si se desea identificar ácidos grasos mediante cromatografía de gases acoplada a la espectrometría de masas (GC-MS).
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S’ha estudiat la bioacumulació de contaminants orgànics persistents en el múscul d’una espècie de peix en dos punts del litoral català: al Port de Barcelona i a la costa de Blanes. Citharus linguatula ha estat escollida per les seves característiques d’hàbitats (està més exposada a la contaminació al ser una espècie bentònica). La metodologia emprada consisteix en la homogeneïtzació amb sulfat de sodi i una extracció assistida amb microones amb n-hexà-acetona(1:1 v/v) durant 20 minuts. Els extractes es netegen i es fraccionen amb una columna cromatogràfica d’alúmina que permet la separació dels extractes en dos fraccions: un amb la majoria dels compostos organoclorats (hexaclorbenzè, DDTs, ciclodiens clorats i policlorbifenils) i l’altre amb els isòmers hexaclorciclohexans i els PAHs. Aquestes dos fraccions són posteriorment analitzades en el GC-MS. S’ha pogut corroborar l’elevada presència de PCBs a Barcelona, així com que en aquest punt de mostreig les espècies estan més exposades a la contaminació per organoclorats. S’ha identificat la presència de DDTs en els dos llocs estudiats. Pel que fa als PAHs s’ha pogut observar que a Barcelona també hi ha més presència d’aquests. Cal destacar que la concentració obtinguda dels compostos no es pot donar com a vàlida per l’existència d’indicis d’errors experimentals o d’injecció.
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En aquest estudi es realitzà eliminació biològica simultània de fòsfor i nitrogen en un Reactor Discontinu Seqüencial (SBR), el qual conté una biomassa enriquida amb Organismes Desnitrificadors Acumuladors de Fòsfor (DPAO) que utilitzen com a única font de carboni l’àcid propiònic i com acceptors d’electrons: nitrit en la fase anòxica i oxigen en l’aeròbica. L’SBR opera amb cicle de 8 h alternant fase anaeròbica, anòxica i aeròbica. El seguiment del sistema es realitzà mitjançant mesures on-line (titrimetria) i off-line (quantificació d’àcid propiònic, nitrit i fòsfor), utilitzant l’HPLC per quantificar l’àcid propiònic i cromatografia iònica per les mesures de nitrit i fòsfor. Amb aquest sistema es pretén augmentar la captació de fòsfor en la fase anòxica fet que s’aconseguí realitzant diferents canvis al reactor per tal de maximitzar el consum de nitrit en aquesta fase, ja fos allargant el temps de fase o augmentant la concentració de biomassa. Aquest experiment ha suposat un augment de la captació de fòsfor (33 mg P-PO4 3-/L), de l’eliminació neta de fòsfor (17 mg P-PO4 3-/L) i de consum de nitrit (27 mg N-NO2-). Per altra banda, es pretenia veure els efectes a curt termini de l’eliminació de la fase aeròbica a partir del seguiment de 2 cicle puntuals i d’un cicle de 32 h sense fase aeròbica. En ambdós casos s’aconseguí una eliminació neta de fòsfor.
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This work is focused on the development of a methodology for the use of chemical characteristic of tire traces to help answer the following question: "Is the offending tire at the origin of the trace found on the crime scene?". This methodology goes from the trace sampling on the road to statistical analysis of its chemical characteristics. Knowledge about the composition and manufacture of tread tires as well as a review of instrumental techniques used for the analysis of polymeric materials were studied to select, as an ansi vi cal technique for this research, pyrolysis coupled to a gas Chromatograph with a mass spectrometry detector (Py-GC/MS). An analytical method was developed and optimized to obtain the lowest variability between replicates of the same sample. Within-variability of the tread was evaluated regarding width and circumference with several samples taken from twelve tires of different brands and/or models. The variability within each of the treads (within-variability) and between the treads (between-variability) could be quantified. Different statistical methods have shown that within-variability is lower than between-variability, which helped differentiate these tires. Ten tire traces were produced with tires of different brands and/or models by braking tests. These traces have been adequately sampled using sheets of gelatine. Particles of each trace were analysed using the same methodology as for the tires at their origin. The general chemical profile of a trace or of a tire has been characterized by eighty-six compounds. Based on a statistical comparison of the chemical profiles obtained, it has been shown that a tire trace is not differentiable from the tire at its origin but is generally differentiable from tires that are not at its origin. Thereafter, a sample containing sixty tires was analysed to assess the discrimination potential of the developed methodology. The statistical results showed that most of the tires of different brands and models are differentiable. However, tires of the same brand and model with identical characteristics, such as country of manufacture, size and DOT number, are not differentiable. A model, based on a likelihood ratio approach, was chosen to evaluate the results of the comparisons between the chemical profiles of the traces and tires. The methodology developed was finally blindly tested using three simulated scenarios. Each scenario involved a trace of an unknown tire as well as two tires possibly at its origin. The correct results for the three scenarios were used to validate the developed methodology. The different steps of this work were useful to collect the required information to test and validate the underlying assumption that it is possible to help determine if an offending tire » or is not at the origin of a trace, by means of a statistical comparison of their chemical profile. This aid was formalized by a measure of the probative value of the evidence, which is represented by the chemical profile of the trace of the tire. - Ce travail s'est proposé de développer une méthodologie pour l'exploitation des caractéristiques chimiques des traces de pneumatiques dans le but d'aider à répondre à la question suivante : «Est-ce que le pneumatique incriminé est ou n'est pas à l'origine de la trace relevée sur les lieux ? ». Cette méthodologie s'est intéressée du prélèvement de la trace de pneumatique sur la chaussée à l'exploitation statistique de ses caractéristiques chimiques. L'acquisition de connaissances sur la composition et la fabrication de la bande de roulement des pneumatiques ainsi que la revue de techniques instrumentales utilisées pour l'analyse de matériaux polymériques ont permis de choisir, comme technique analytique pour la présente recherche, la pyrolyse couplée à un chromatographe en phase gazeuse avec un détecteur de spectrométrie de masse (Py-GC/MS). Une méthode analytique a été développée et optimisée afin d'obtenir la plus faible variabilité entre les réplicas d'un même échantillon. L'évaluation de l'intravariabilité de la bande de roulement a été entreprise dans sa largeur et sa circonférence à l'aide de plusieurs prélèvements effectués sur douze pneumatiques de marques et/ou modèles différents. La variabilité au sein de chacune des bandes de roulement (intravariabilité) ainsi qu'entre les bandes de roulement considérées (intervariabilité) a pu être quantifiée. Les différentes méthodes statistiques appliquées ont montré que l'intravariabilité est plus faible que l'intervariabilité, ce qui a permis de différencier ces pneumatiques. Dix traces de pneumatiques ont été produites à l'aide de pneumatiques de marques et/ou modèles différents en effectuant des tests de freinage. Ces traces ont pu être adéquatement prélevées à l'aide de feuilles de gélatine. Des particules de chaque trace ont été analysées selon la même méthodologie que pour les pneumatiques à leur origine. Le profil chimique général d'une trace de pneumatique ou d'un pneumatique a été caractérisé à l'aide de huitante-six composés. Sur la base de la comparaison statistique des profils chimiques obtenus, il a pu être montré qu'une trace de pneumatique n'est pas différenciable du pneumatique à son origine mais est, généralement, différenciable des pneumatiques qui ne sont pas à son origine. Par la suite, un échantillonnage comprenant soixante pneumatiques a été analysé afin d'évaluer le potentiel de discrimination de la méthodologie développée. Les méthodes statistiques appliquées ont mis en évidence que des pneumatiques de marques et modèles différents sont, majoritairement, différenciables entre eux. La méthodologie développée présente ainsi un bon potentiel de discrimination. Toutefois, des pneumatiques de la même marque et du même modèle qui présentent des caractéristiques PTD (i.e. pays de fabrication, taille et numéro DOT) identiques ne sont pas différenciables. Un modèle d'évaluation, basé sur une approche dite du likelihood ratio, a été adopté pour apporter une signification au résultat des comparaisons entre les profils chimiques des traces et des pneumatiques. La méthodologie mise en place a finalement été testée à l'aveugle à l'aide de la simulation de trois scénarios. Chaque scénario impliquait une trace de pneumatique inconnue et deux pneumatiques suspectés d'être à l'origine de cette trace. Les résultats corrects obtenus pour les trois scénarios ont permis de valider la méthodologie développée. Les différentes étapes de ce travail ont permis d'acquérir les informations nécessaires au test et à la validation de l'hypothèse fondamentale selon laquelle il est possible d'aider à déterminer si un pneumatique incriminé est ou n'est pas à l'origine d'une trace, par le biais d'une comparaison statistique de leur profil chimique. Cette aide a été formalisée par une mesure de la force probante de l'indice, qui est représenté par le profil chimique de la trace de pneumatique.
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A novel approach to measure carbon dioxide (CO2) in gaseous samples, based on a precise and accurate quantification by (13)CO2 internal standard generated in situ is presented. The main goal of this study was to provide an innovative headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable in the routine determination of CO2. The main drawback of the GC methods discussed in the literature for CO2 measurement is the lack of a specific internal standard necessary to perform quantification. CO2 measurement is still quantified by external calibration without taking into account analytical problems which can often occur considering gaseous samples. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in situ an internal labeled standard gas ((13)CO2) on the basis of the stoichiometric formation of CO2 by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH(13)CO3). This method allows a precise measurement of CO2 concentration and was validated on various human postmortem gas samples in order to study its efficiency.
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By means of ethereal washing of insect pheromone glands of female moths, GC-MS detection along with microchemical reactions and electroantennogram (EAG) survey, six economically important insect species were targeted for pheromone identification. The discovery of a natural pheromone inhibitor, chemo-selectivity and species isolation by pheromone will be described. The modified triple bond migration and triethylamine liganded vinyl cuprate were applied for achiral pheromone synthesis in double bond formation. Some optically active pheromones and their stereoisomers were synthesized through chiral pool or asymmetric synthesis. Some examples of chiral recognition of insects towards their chiral pheromones will be discussed. A CaH2 and silica gel catalyzed Sharpless Expoxidation Reaction was found in shortening the reaction time.
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Limited information is available regarding the methodology required to characterize hashish seizures for assessing the presence or the absence of a chemical link between two seizures. This casework report presents the methodology applied for assessing that two different police seizures were coming from the same block before this latter one was split. The chemical signature was extracted using GC-MS analysis and the implemented methodology consists in a study of intra- and inter-variability distributions based on the measurement of the chemical profiles similarity using a number of hashish seizures and the calculation of the Pearson correlation coefficient. Different statistical scenarios (i.e., a combination of data pretreatment techniques and selection of target compounds) were tested to find the most discriminating one. Seven compounds showing high discrimination capabilities were selected on which a specific statistical data pretreatment was applied. Based on the results, the statistical model built for comparing the hashish seizures leads to low error rates. Therefore, the implemented methodology is suitable for the chemical profiling of hashish seizures.
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A gas chromatography-mass spectrometry (GC-MS) method is presented which allows the simultaneous determination of the plasma concentrations of the levo-alpha-acetylmethadol (LAAM) and of its active metabolites (NorLAAM and DiNorLAAM), after derivatization with the reagent trifluoroacetic anhydride (TFAA). No interferences from endogenous compounds were observed following the extraction of plasma samples from 11 different human subjects. The standard curves were linear over a working range of 5-200ng/ml for the three compounds. Recoveries measured at three concentrations ranged from 47 to 67% for LAAM, from 50 to 69% for NorLAAM and from 28 to 50% for DiNorLAAM. Intra- and interday coefficients of variation determined at three concentrations ranged from 5 to 13% for LAAM, from 3 to 9% for NorLAAM and from 5 to 13% for DiNorLAAM. The limits of quantitation of the method were found to be 4ng/ml for the three compounds. No interference was noted from methadone. This sensitive and specific analytical method could be useful for assessing the in vivo relationship between LAAM's blood levels, clinical efficacy and/or cardiotoxicity
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La determinació de compostos orgànics contaminants en aigües residuals d’origen urbà i industrial és un tema que ha suscitat un creixent interès, tant des del punt de vista del problema mediambiental que es deriva de l’abocament d’aquestes aigües al medi aquàtic públic com des de la perspectiva de reutilització de les aigües tractades en processos industrials. La majoria d’aquests contaminants no s’eliminen completament en plantes de tractament d’aigües convencionals, pel que s’han de controlar. Aquest fet implica desenvolupar nous processos de tractament que permetin millorar l'eficiència de l'eliminació de les plantes de tractament convencionals. Per tal d'investigar la presència d'aquests compostos contaminants a baixes concentracions és necessari desenvolupar nous mètodes analítics altament sensibles. En el nostre projecte s'han desenvolupat diferents mètodes analítics per determinar compostos orgànics contaminants en aigües residuals provinents de plantes de tractament d'aigües industrials, urbanes i plantes potabilitzadores, utilizant principalment la microextracció en fase sòlida (SPME) seguida de la cromatografia de gasos acoblada a un espectròmetre de masses (GC-MS). S'ha estudiat la presència de diferents famílies de compostos en aquestes aigües, com són: ftalats, amines alifàtiques primàries i nitrosamines. A més a més, s'han desenvolupat mètodes analítics per determinar amines alifàtiques primàries en llots actius provinents de diferents tipus de plantes de tractament d'aigües i plantes potabilitzadores.
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This study presents a classification criteria for two-class Cannabis seedlings. As the cultivation of drug type cannabis is forbidden in Switzerland, law enforcement authorities regularly ask laboratories to determine cannabis plant's chemotype from seized material in order to ascertain that the plantation is legal or not. In this study, the classification analysis is based on data obtained from the relative proportion of three major leaf compounds measured by gas-chromatography interfaced with mass spectrometry (GC-MS). The aim is to discriminate between drug type (illegal) and fiber type (legal) cannabis at an early stage of the growth. A Bayesian procedure is proposed: a Bayes factor is computed and classification is performed on the basis of the decision maker specifications (i.e. prior probability distributions on cannabis type and consequences of classification measured by losses). Classification rates are computed with two statistical models and results are compared. Sensitivity analysis is then performed to analyze the robustness of classification criteria.
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Introduction: Rotenone is a botanical pesticide derived from extracts of Derris roots, which is traditionally used as piscicide, but also as an industrial insecticide for home gardens. Its mechanism of action is potent inhibition of mitochondrial respiratory chain by uncoupling oxidative phosphorylation by blocking electron transport at complex-I. Despite its classification as mild to moderately toxic to humans (estimated LD50, 300-500 mg/kg), there is a striking variety of acute toxicity of rotenone depending on the formulation (solvents). Human fatalities with rotenone-containing insecticides have been rarely reported, and a rapid deterioration within a few hours of the ingestion has been described previously in one case. Case report: A 49-year-old Tamil man with a history of asthma, ingested 250 mL of an insecticide containing 1.24% of rotenone (3.125 g, 52.1-62.5 mg/kg) in a suicide attempt at home. The product was not labeled as toxic. One hour later, he vomited repeatedly and emergency services were alerted. He was found unconscious with irregular respiration and was intubated. On arrival at the emergency department, he was comatose (GCS 3) with fixed and dilated pupils, and absent corneal reflexes. Physical examination revealed hemodynamic instability with hypotension (55/30 mmHg) and bradycardia (52 bpm). Significant laboratory findings were lactic acidosis (pH 6.97, lactate 17 mmol/L) and hypokalemia (2 mmol/L). Cranial computed tomography (CT) showed early cerebral edema. A single dose of activated charcoal was given. Intravenous hydration, ephedrine, repeated boli of dobutamine, and a perfusor with 90 micrograms/h norepinephine stabilized blood pressure temporarily. Atropine had a minimal effect on heart rate (58 bpm). Intravenous lipid emulsion was considered (log Pow 4.1), but there was a rapid deterioration with refractory hypotension and acute circulatory failure. The patient died 5h after ingestion of the insecticide. No autopsy was performed. Quantitative analysis of serum performed by high-resolution/accurate mass-mass spectrometry and liquid chromatography (LC-HR/AM-MS): 560 ng/mL rotenone. Other substances were excluded by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS/MS). Conclusion: The clinical course was characterized by early severe symptoms and a rapidly fatal evolution, compatible with inhibition of mitochondrial energy supply. Although rotenone is classified as mild to moderately toxic, physicians must be aware that suicidal ingestion of emulsified concentrates may be rapidly fatal. (n=3): stridor, cyanosis, cough (one each). Local swelling after chewing or swallowing soap developed at the earliest after 20 minutes and persisted beyond 24 hours in some cases. Treatment with antihistamines and/or steroids relieved the symptoms in 9 cases. Conclusion: Bar soap ingestion by seniors carries a risk of severe local reactions. Half the patients developed symptoms, predominantly swellings of tongue and/or lips (38%). Cognitive impairment, particularly in the cases of dementia (37%), may increase the risk of unintentional ingestion. Chewing and intraoral retention of soap leads to prolonged contact with the mucosal membranes. Age-associated physiological changes of oral mucosa probably promote the irritant effects of the surfactants. Medical treatment with antihistamines and corticosteroids usually leads to rapid decline of symptoms. Without treatment, there may be a risk of airway obstruction.
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Estimating the time since the last discharge of firearms and/or spent cartridges may be a useful piece of information in forensic firearm-related cases. The current approach consists of studying the diffusion of selected volatile organic compounds (such as naphthalene) released during the shooting using solid phase micro-extraction (SPME). However, this technique works poorly on handgun car-tridges because the extracted quantities quickly fall below the limit of detection. In order to find more effective solutions and further investigate the aging of organic gunshot residue after the discharge of handgun cartridges, an extensive study was carried out in this work using a novel approach based on high capacity headspace sorptive extraction (HSSE). By adopting this technique, for the first time 51 gunshot residue (GSR) volatile organic compounds could be simultaneously detected from fired handgun cartridge cases. Application to aged specimens showed that many of those compounds presented significant and complementary aging profiles. Compound-to-compound ratios were also tested and proved to be beneficial both in reducing the variability of the aging curves and in enlarging the time window useful in a forensic casework perspective. The obtained results were thus particularly promising for the development of a new complete forensic dating methodology.
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Determining the time since discharge of spent cartridges found on a crime scene may be very useful in firearm investigations. The potential of small calibre munitions was barely studied before and this work did therefore focus on that problematic. The first step was to optimize the detection potential of solidphase microextraction (SPME) followed by gas chromatography coupled to a mass spectrometry detector (GC/MS). This allowed determining the organic volatile composition of empty cartridges immediately after a gunshot. Identification of 32 detected compounds was confirmed by the analysis of reference substances. Preliminary aging studies over 32 hours were carried out on selected target compounds to evaluate their potential for the dating of shotguns.
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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.