2-Nitrofluorene is a model representative of nitrated polycyclic aromatic hydrocarbons (NPAH) which belongs to a group of mutagens and carcinogens. Interaction of DNA with genotoxic 2-nitrofluorene was monitored by an electrochemical DNA biosensor made of a glassy carbon electrode (GCE) and low molecular weight DNA from salmon sperm. Techniques used are electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and square-wave voltammetry (SWV). Using the EIS technique, no damage to DNA, which would cause strand breaks in DNA, was observed, whereas using the CV technique, the intercalation of NF to the structure of DNA was observed, leading to the formation of a NF-DNA complex. The intercalation results in a reduction of electroactive sites which can be oxidized. It was verified using the SWV technique, by which a decrease of the peak heights of adenosine and guanosine was observed. Because of the dangerous effect of NF on the structure of DNA, an electroanalytical method for its determination was developed. An applicability of the method was successfully tested on a model sample of sand. For the development of the technique, differential pulse voltammetry (DPV) was used in a mixture of the Britton-Robinson buffer of pH 7.0 and ethanol in a ratio of 7:3 (v/v) and with a periodic...

Les hydrocarbures aromatiques polycycliques (HAP) sont des polluants organiques persistants potentiellement mutagènes et cancérigènes. Leur transfert de l’atmosphère vers les écosystèmes, notamment vers les plantes, conditionne leur entrée dans les chaines alimentaires mais les modalités de ce transfert restent encore mal connues. L’objectif de ce travail était donc de caractériser le transfert et d’identifier les effets biologiques des HAP atmosphériques sur un système sol-plante-microorganismes symbiotiques.Un dispositif expérimental a été conçu afin de recréer en laboratoire une pollution atmosphérique par les HAP avec comme HAP modèle le phénanthrène (PHE). Le dispositif a fait l’objet d’une validation et d’une calibration élaborée de manière originale par une double approche mêlant l’expérimental à la simulation mathématique. Les niveaux d’exposition en polluant (150 µg m-3), contrôlés par des échantillonneurs passifs, se sont avérés pertinents par rapport aux conditions in situ. Ce dispositif a donc été utilisé pour exposer durant un mois des microsystèmes sol-plante-microorganismes au PHE par voie atmosphérique.Les différentes études ont mis en évidence un transfert du PHE depuis l’atmosphère vers tous les compartiments du microsystème, avec une accumulation majeure vers les feuilles de trèfle ou de ray-grass (respectivement 170 et 70 µg g־ ¹MS) et un transfert phloémien vers les racines est suggéré. Chez le trèfle, la mycorhization n’a pas été affectée, tandis que le nombre de nodules actifs a diminué de manière significative. Contrairement aux racines, la biomasse aérienne du trèfle a été significativement affectée (environ – 25%) par l’exposition au PHE atmosphérique, suggérant un impact sur le métabolisme carboné de la plante. Une expérience de marquage des trèfles au ¹³C-CO2 a effectivement montré un impact négatif du PHE atmosphérique sur la croissance, l’allocation de biomasse et l’allocation carbonée. Pour conclure, ces études ont permis non seulement de caractériser les effets biologiques et physiologiques des HAP atmosphériques sur les végétaux mais également de proposer l’utilisation du potentiel mycorhizien comme indicateur de pollution atmosphérique par les HAP. / Polycyclic aromatic hydrocarbons (PAHs) are persistent organic pollutants potentially mutagenic and carcinogenic. Transfer from the atmosphere to ecosystems, especially to plants, conditioning their entry into food chains, but the terms of this transfer are still poorly understood. The aim of this study was to characterize the transfer and identify the biological effects of atmospheric PAHs on soil-plant-symbiotic microorganisms.An experimental device was designed to recreate in the laboratory air pollution with phenanthrene (PHE) as a model PAH. The device was been validated and a calibration developed in an original way by a dual approach combining the experimental mathematical simulation. The levels of exposure to pollutant (150 mg m־³), controlled by passive samplers, were relevant with field conditions. This device has been used to expose a month of the soil-plant micro-organisms in the PHE through the air.Various studies have demonstrated a transfer of PHE from the atmosphere to all compartments of the microsystem, with a major accumulation to leaves in clover or ryegrass (respectively 170 and 70 µg g ־¹ dry weight) and a phloemic transfer to the roots is suggested. In clover, mycorrhization was not affected, while the number of active nodules decreased significantly. Unlike roots, aboveground biomass of clover was significantly affected (approximately – 25%) by exposure to air PHE, suggesting an impact on the carbon metabolism of the plant. A labelling experiment with ¹³C- CO2 in clover has actually shown a negative impact of PHE air on growth, biomass and carbon allocation.In conclusion, these studies have not only characterized the biological and physiological effects of atmospheric PAHs on plants but also proposed the use of mycorrhizal potential as an indicator of air pollution by PAHs.

Les hydrocarbures aromatiques polycyliques (HAPs) figurent parmi les polluants organiques persistants majeurs des sols pollués et présentent une toxicité avérée vis-à-vis de l'homme et des écosystèmes. Parmi les méthodes de remédiation des sols pollués par les HAPs, la phytoremédiation assistée par les champignons mycorhiziens à arbuscules (CMA), pourrait représenter une alternative innovante, écologique et économique. L'utilisation des mycorhizes comme outil de phytoremédiation des sols pollués présente plusieurs avantages dont une meilleure tolérance à la toxicité des HAPs, une meilleure nutrition hydrique et minérale ainsi qu'une meilleure dissipation des HAPs. De rares études ont décrit l'impact des HAPs sur le développement des CMA en lien avec une péroxydation lipidique et une perturbation des teneurs en lipides du CMA, mais ni les cibles d'action de ces polluants au niveau du métabolisme lipidique, ni le rôle de ces modifications dans sa tolérance aux HAPs et dans leur dissipation n'ont été étudiés. C'est pourquoi, le premier objectif de ce travail vise tout d'abord à comprendre l'impact des HAPs sur le métabolisme lipidique. Le radiomarquage par l'acétate [1-¹⁴C] a permis de montrer une perturbation de la biosynthèse des lipides membranaires du CMA extra-racinaire. D'autre part, nos résultats montrent que les HAPs affectent la nutrition phosphatée. Par ailleurs, la capacité des mycorhizes à dégrader et à bioaccumuler le benzo[a]pyrène est démontrée. Enfin, l'implication du métabolisme des lipides de réserve (les triacylglycérols) du mycélium extra-racinaire dans la régénération des membranes altérées, la lutte contre le stress oxydant induit par les HAPs et dans leur métabolisation/bioaccumulation est discutée. / Polycyclic aromatic hydrocarbons (PAHs) are among the major persistent organic pollutant frequently found in the polluted soils and are harmful for human health and its environment. To clean-up the PAHs polluted soils, phytoremediation assisted by arbuscular mycorrhizal fungi (AMF) could represent an innovative, ecological and cost-effective alternative. The use of mycorrhizas, as phytoremediation tool, has several advantages including increased tolerance to the pollutant toxicity, improved water and mineral nutrition as well as a better pollutant dissipation. Few studies have described the impact of PAHs on the AMF development related with lipid peroxidation and total lipid content disturbance. However, so far neither the target action of these pollutants on the metabolism, nor the role of these lipid changes in PAH tolerance and in their dissipation have been studied. Therefore, the present work aims firstly to improve our understanding of the PAHs impact on the CMA lipid metabolism. Thanks to radiolabeling experiments with [1-¹⁴C] acetate, our results showed a disruption of the membrane lipid biosynthesis pathways in the AMF extraradical mycelium, grown in the presence of PAHs. Secondly, it was highlighted that the PAHs affectef the phosphate nutrition. Finally, the mycorrhizas abilities to degrade and to bioaccumulate the benzo[a]pyrene, were pointed out. The involvement of extraradical mycelium storage lipid (triacyglycerols) metabolism in the membrane regeneration, the fight against the PAH induced-oxidative stress and the PAH metabolism/bioaccumulation is discussed.

Classés parmi les Polluants Organiques Persistants, les Hydrocarbures Aromatiques Polycycliques (HAP) sont des composés ubiquitaires dans l'environnement, auxquels l'Homme est exposé principalement via l'ingestion d'aliments contaminés. Les HAP sont connus depuis les années 1990 comme pouvant être neurotoxiques tant chez l'Homme que chez l'animal. Le transfert des HAP entre la mère et le foetus via le placenta ainsi que la présence de ces composés dans le lait maternel ont été montrés à plusieurs reprises, posant ainsi la question du risque lié à une exposition survenant lors de phases précoces du développement de l'individu. Parce que ce risque n'a été que partiellement étudié, le travail de thèse présenté dans ce manuscrit a eu pour objectif d'évaluer la toxicité à court et à long terme pour le système nerveux en développement, d'un mélange de 16 HAP ingéré par la rate gestante et/ou allaitante. Les HAP ont été administrés via un aliment contaminé à deux doses, 2 et 200 µg/kg/jour La dose la plus faible correspond aux niveaux de contamination environnementale via l'alimentation de la mère pendant les périodes de gestation et/ou d'allaitement. Les résultats montrent que l'exposition périnatale au mélange de HAP n'a pas induit d'effets à court terme sur le développement neuromoteur et sensoriel des jeunes rats. En revanche, une augmentation à long terme des niveaux d'activité et d'anxiété a été relevée chez les animaux exposés. Par ailleurs, des modifications du métabolisme énergétique cérébral, évalué par l'activité enzymatique de la cytochrome oxydase sur des coupes de cerveaux prélevés à différents âges ont été observées, notamment au niveau du système limbique. La mesure des concentrations de HAP dans le compartiment cérébral des ratons a montré la présence de l'ensemble des molécules mères, y compris chez les animaux témoins, ce qui laisse supposer l'existence d'un bruit de fond environnemental non négligeable dans ce type d'étude. Finalement, plusieurs facteurs modulent la toxicité induite, parmi lesquelles la période d'exposition, et l'administration d'un mélange et non d'une molécule seule. En conclusion, ce travail a permis de mettre en évidence, chez le rat, une neurotoxicité retardée suite à une exposition précoce à un mélange de 16 HAP tant sur le plan comportemental que métabolique, ce qui pose la question du risque pour l'Homme, et en particulier pour l'individu en développement, d'une exposition à ce type de composés / Compounds in the environment to which human is exposed mainly through ingestion of contaminated food. PAHs are known since the 1990s as being neurotoxic both in humans and in animals. PAH transfer between mother and fetus through the placenta, and the presence of these compounds in breast milk have been shown, thus raising the question of risk exposure occurring during early stages of development of the individual. Because this risk was only partially studied, the thesis presented in this manuscript was designed to assess the short-term and long-term toxicity for the developing nervous system, of a mixture of 16 PAHs ingested by the pregnant and / or breastfeeding rat. PAHs were administered via a contaminated food at two doses, 2 and 200 µg/kg /day dose. The lowest one corresponds to the levels of environmental contamination via the mother's diet during gestation and/or lactation. The results show that perinatal exposure to the mixture of PAHs did not induce short-term effects on neuromotor and sensory development on pups. In contrast, a long-term increase in activity and anxiety levels was observed in the exposed animals. In addition, changes in cerebral energy metabolism, as assessed by the enzymatic activity of cytochrome oxidase on brain sections taken at different ages were observed, particularly in the limbic system. Measures of the concentrations of PAHs in the pup brain compartment showed the presence of all the parent compounds, including control animals, suggesting the existence of an environmental noise significant. Finally, several factors modulate PAH toxicity, including the exposure period, and the administration of a mixture instead of a single molecule. In conclusion, this work has highlighted, in rats, delayed neurotoxicity due to early exposure to a mixture of 16 PAHs, which raises the question of risk to humans, and in particular for the individual developing exposure to such compounds

Dans le cadre de la protection de l’environnement et du consommateur, CTC effectue des tests enchimie analytique sur de nombreux paramètres en matrices aqueuses, cuir et textile. Les nouvelles substancesmises sur le marché ainsi que les réglementations évoluant sans cesse, le développement de nouvellesméthodes d’analyses est donc nécessaire.Plusieurs méthodes analytiques ont ainsi été développées. Pour l’analyse des rejets d’effluents industriels desinstallations classées et pour l’analyse d’innocuité de produits utilisant le cuir ou le textile (chaussures,maroquinerie, prêt-à-porter…).Les chloroalcanes ont été dosés en chromatographie gazeuse (GC) associée à la spectrométrie de masse (MS)utilisant l’ionisation chimique, à la fois en matrices aqueuses (limite de quantification, LQ, à 0,6 μg/l) et sur lescuirs (LQ à 2 mg/kg).Une analyse des alkylphénols et alkylphénols ethoxylates a été développée pour les matrices aqueuses parGC/MS (LQ à 0,05 μg/l).Plusieurs familles de retardateurs de flammes ont ensuite été étudiées. Les polybromodiphénylethers peuventêtre dosés dans les eaux (LQ<0,05 µl) et le cuir (LQ <= µg/kg), par GC/MS en ionisationchimique.L’hexabromocyclododécane et des organophosphates, par chromatographie liquide et spectrométrie de masseen tandem pour des matrices textiles (LQ à 6 mg/kg). Des hydrocarbures aromatiques polycycliques dans le cuir ont ensuite été analysés par GC/MS-MS (LQ à 250 μg/kg).Enfin, une méthode multirésidus portant sur plusieurs familles de micropolluants organiques a été mise aupoint en GC/MS pour les rejets d’effluents (LQ <0,1 µg/l) / Taking in account the increasing needs and demands in environmental and consumer protection, CTCis always seeking improvement in analytical methods and development of new ones dealing with leather,fabrics and aqueous samples. In this thesis, several new methods were developed to be able to handleanalytical requests dealing with leather and textile materials being parts of shoes, clothes and other leathergoods.A GC/MS method using chemical ionization was developed to detect short polychlorinated alkanes down to aconcentration of 0.6 μg/L in aqueous sample and 2 mg/kg in leather samples. Alkylphenols and theirethoxylates were similarly determined by GC/MS down to 0.05 μg/L.Flame retardants are another large class of chemicals becoming suspicious. Polybromodiphenylethers weredetermined in aqueous samples and leathers. The respective GC/MS highest limits of quantification (LOQ)were0.05 µg/l and 80 μg/kg. Other members of this class are hexabromocyclododecane andorganophosphates. Both were determined by LC/MS-MS with LOQ of about 6 mg/kg.Carcinogenic polyaromatic hydrocarbons were also determined in leather samples using GC/MS-MS down to250 μg/kg.The last improved GC/MS analytical method was handling sewage sludge seeking multi residues of organicpolluants down to the 0.1 µg/l level or below. The analytical performances developed or improved allowedfor an efficient and useful control of the various sample received from the CTC customers and followinginternational quality rules

Syftet med arbetet har varit att undersöka hur arbetsmiljön och innemiljön med avseende på luftkvalitet har förändrats ombord fartyget M/S Aurora af Helsingborg efter konvertering från dieselelektrisk- till batteridrift. Resultatet har sedan jämförts med Arbetsmiljöverkets hygieniska gränsvärden, WHOs riktlinjer och tidigare mätning på Aurora som utfördes 2014, innan konverteringen till batteridrift. Då bestod framdrivningen av fyra Wärtsilä-Vasa 6R32E dieselmotorer som körde på miljödiesel. Under sju dagar i mars 2019, från nionde till sextonde, har mätdata samlats in på fartyget Aurora genom olika passiva provtagare för: Polycykliska aromatiska kolväten (PAH), lättflyktiga organiska ämnen (TVOC), temperatur, relativ luftfuktighet, partiklar, SO2 och NO2. Resultaten av mätvärdena visade att det är bra Luftkvalitet ombord på fartyget och att innemiljön blivit bättre sedan konverteringen. Alla uppmätta halter låg långt under de hygieniska gränsvärdena som Arbetsmiljöverket tagit fram. Nivåerna låg även under riktlinjerna bortsett från TVOC i separatorrummet där halterna är betydligt högre än riktvärdet. Arbetsuppgifterna ombord Aurora har förändrats till det bättre sedan konverteringen med bland annat mindre hantering av oljeprodukter. / The purpose of this study is to examine how the work environment and indoor air quality has changed onboard M/S Aurora af Helsingborg after the conversion from diesel electric to battery. The results have been compared to Swedish Work Environment Authority (Arbetsmiljöverket) hygienic exposure limits, World Health Organizations (WHO) guidelines and previous measurements from 2014 done on Aurora before the conversion to battery drive. At that time Aurora was propelled by four Wärtsilä-Vasa 6R32E diesel engines running on environmental diesel. During seven days in March from 9th to 16th 2019, data was collected on the vessel Aurora by different types of passive samplers: Polycyclic aromatic hydrocarbons (PAH), benzo(a)pyrene, total volatile organic substances (TVOC), benzene, temperature, relative humidity, particulate matter (PM), SO2, NO2. The result from the data collected showed that the indoor air quality onboard and the inside environment has improved after the conversion. All measured data were much lower than the hygienic limit values that Swedish Work Environment Authority has set. The values of the data were also lower than recommendations except from TVOC in purifier room. The duties on board Aurora has changed for the better since the conversion, including less management of oil products.

O material particulado nas frações fina e inalável (MP2,5 e MP10) para três cidades da América Latina (São Paulo Brasil, Lima Peru e Medellín Colômbia) foi analisado quimicamente para a avaliação de fontes de poluição atmosférica e dos riscos à saúde. Em São Paulo, uma campanha extensiva foi realizada ao longo de 2014 no campus da Universidade de São Paulo, com coletas de MP2,5 e MP10. Campanhas intensivas (no inverno) foram realizadas em São Paulo nos anos de 2010, 2013 e 2014, e em Lima e Medellín no ano de 2010. As espécies hidrocarbonetos policíclicos aromáticos (HPA), íons orgânicos e inorgânicos, e monossacarídeos foram determinadas por técnicas cromatográficas; as espécies carbonáceas (carbono orgânico e elementar) foram determinadas por análise termo-óptica. Os elementos foram determinados por espectrometria de massas com plasma indutivamente acoplado. Os riscos associados à exposição ao material particulado com base nas concentrações de HPA foram avaliados com os índices benzo(a)pireno equivalente (BaPE) e de risco de câncer de pulmão (RCPV). Nas campanhas intensivas de 2010, a concentração média do MP10 foi mais elevada em São Paulo do que nos outros dois sítios, 75% das amostras apresentaram concentrações acima do recomendado pela Organização Mundial da Saúde. A razão levoglucosano/manosano para São Paulo sugeriu a grande contribuição da queima da cana-de-açúcar, que em 2010 ocorreu em 70 % dos municípios do estado. Elementos relacionados às emissões veiculares (Fe, Cu) apresentaram maiores concentrações também em São Paulo. As e Pb tiveram concentrações mais elevadas em Medellín, atribuídos às emissões industriais. A concentração de Ni foi mais elevada em Lima, a espécie é associada às emissões de instalações de fundição de metal e à combustão de óleo em navios. Altos índices de BaPE e RCPV foram observados na maioria das amostras em São Paulo no ano de 2014, alcançando valores críticos no inverno (acima de 1 ng m-3 e 10-4, respectivamente). Além disso, as concentrações de HPA e traçadores de queima de biomassa foram mais elevadas no inverno. As espécies traçadoras de fontes veiculares também foram mais abundantes na campanha intensiva (inverno) devido à menor dispersão de poluentes, menos chuvas e maior frequência de inversões térmicas. A fatoração de matriz positiva permitiu uma melhor compreensão das contribuições de fontes de emissão que afetam o sítio (ressuspensão do solo, emissões industriais, emissão veicular, queima de biomassa e formação secundária). Os resultados enfatizaram a contribuição das emissões veiculares e uma contribuição significativa da queima de biomassa na estação seca (30,9 e 18,3 %, respectivamente). A maior parte do material particulado foi relacionada às fontes locais (veiculares), além da influência da queima de biomassa (cana-de-açúcar e queimas urbanas). Assim, os resultados destacaram a importância e a contribuição das atividades humanas na qualidade do ar nos três sítios latino-americanos. / The particulate matter in the fine and inhalable fractions (PM2.5 and PM10) collected in three Latin American cities (São Paulo, Brazil; Lima, Peru; and Medellín, Colombia) was chemically analysed in order to investigate the sources of atmospheric pollution and related health risks. In São Paulo, a year-round extensive campaign (2014) was conducted at the University of São Paulo campus (PM2.5 and PM10). Intensive campaigns were performed in São Paulo (2010, 2013 and 2014) and in Lima and Medellín (2010). The species such as polycyclic aromatic hydrocarbons (PAHs), organic and inorganic ions and the monosaccharides were determined by chromatographic techniques. The carbonaceous species (organic and elemental carbon) were determined by thermal-optical analysis. Trace elements were determined by inductively coupled plasma mass spectrometry. The associated risks to particulate matter exposure based on PAH concentrations were assessed with the indexes benzo[a]pyrene equivalent (BaPE) and lung cancer risk (LCR). In 2010, PM10 average concentration was higher in São Paulo than in the other two sites; 75 % of the samples presented concentrations above that recommended by World Health Organization. Levoglucosan/mannosan ratios for São Paulo samples suggested sugarcane burning; in 2010 it occurred in 70 % of São Paulo state municipalities. Vehicular related elements (Fe and Cu) also presented higher concentrations in São Paulo. As and Pb concentrations were higher in Medellín, attributed to industrial emissions. Ni was abundant in Lima atmosphere and associated to emissions from metal smelting facilities and ship heavy oil combustion. High BaPE and LCR were observed in most of the samples in São Paulo in the year of 2014, reaching critical values in the wintertime (above 1 ng m-3 and 10-4, respectively). Also, PAHs and biomass burning tracers concentrations were higher in this season. The vehicular tracer species were also more abundant in the intensive campaign (wintertime) suggesting the lower dispersion conditions, less rainfall and higher frequency of thermal inversions in that period. Positive matrix factorization provided a better comprehension over the contribution sources affecting the site; five different factors were identified: road dust, industrial emissions, vehicular exhaust, biomass burning and secondary formation. The results emphasized the contribution of vehicular emissions and the significant input from biomass combustion in the dry season (30,9 and 18,3 %, respectively). Most of the particulate matter was due to local sources (vehicular), besides the influence of pre-harvest sugarcane and urban biomass burning. Thus, the results emphasize the importance and contribution of the anthropogenic activities in the air quality for the three latin american cities.

O material particulado nas frações fina e inalável (MP2,5 e MP10) para três cidades da América Latina (São Paulo Brasil, Lima Peru e Medellín Colômbia) foi analisado quimicamente para a avaliação de fontes de poluição atmosférica e dos riscos à saúde. Em São Paulo, uma campanha extensiva foi realizada ao longo de 2014 no campus da Universidade de São Paulo, com coletas de MP2,5 e MP10. Campanhas intensivas (no inverno) foram realizadas em São Paulo nos anos de 2010, 2013 e 2014, e em Lima e Medellín no ano de 2010. As espécies hidrocarbonetos policíclicos aromáticos (HPA), íons orgânicos e inorgânicos, e monossacarídeos foram determinadas por técnicas cromatográficas; as espécies carbonáceas (carbono orgânico e elementar) foram determinadas por análise termo-óptica. Os elementos foram determinados por espectrometria de massas com plasma indutivamente acoplado. Os riscos associados à exposição ao material particulado com base nas concentrações de HPA foram avaliados com os índices benzo(a)pireno equivalente (BaPE) e de risco de câncer de pulmão (RCPV). Nas campanhas intensivas de 2010, a concentração média do MP10 foi mais elevada em São Paulo do que nos outros dois sítios, 75% das amostras apresentaram concentrações acima do recomendado pela Organização Mundial da Saúde. A razão levoglucosano/manosano para São Paulo sugeriu a grande contribuição da queima da cana-de-açúcar, que em 2010 ocorreu em 70 % dos municípios do estado. Elementos relacionados às emissões veiculares (Fe, Cu) apresentaram maiores concentrações também em São Paulo. As e Pb tiveram concentrações mais elevadas em Medellín, atribuídos às emissões industriais. A concentração de Ni foi mais elevada em Lima, a espécie é associada às emissões de instalações de fundição de metal e à combustão de óleo em navios. Altos índices de BaPE e RCPV foram observados na maioria das amostras em São Paulo no ano de 2014, alcançando valores críticos no inverno (acima de 1 ng m-3 e 10-4, respectivamente). Além disso, as concentrações de HPA e traçadores de queima de biomassa foram mais elevadas no inverno. As espécies traçadoras de fontes veiculares também foram mais abundantes na campanha intensiva (inverno) devido à menor dispersão de poluentes, menos chuvas e maior frequência de inversões térmicas. A fatoração de matriz positiva permitiu uma melhor compreensão das contribuições de fontes de emissão que afetam o sítio (ressuspensão do solo, emissões industriais, emissão veicular, queima de biomassa e formação secundária). Os resultados enfatizaram a contribuição das emissões veiculares e uma contribuição significativa da queima de biomassa na estação seca (30,9 e 18,3 %, respectivamente). A maior parte do material particulado foi relacionada às fontes locais (veiculares), além da influência da queima de biomassa (cana-de-açúcar e queimas urbanas). Assim, os resultados destacaram a importância e a contribuição das atividades humanas na qualidade do ar nos três sítios latino-americanos. / The particulate matter in the fine and inhalable fractions (PM2.5 and PM10) collected in three Latin American cities (São Paulo, Brazil; Lima, Peru; and Medellín, Colombia) was chemically analysed in order to investigate the sources of atmospheric pollution and related health risks. In São Paulo, a year-round extensive campaign (2014) was conducted at the University of São Paulo campus (PM2.5 and PM10). Intensive campaigns were performed in São Paulo (2010, 2013 and 2014) and in Lima and Medellín (2010). The species such as polycyclic aromatic hydrocarbons (PAHs), organic and inorganic ions and the monosaccharides were determined by chromatographic techniques. The carbonaceous species (organic and elemental carbon) were determined by thermal-optical analysis. Trace elements were determined by inductively coupled plasma mass spectrometry. The associated risks to particulate matter exposure based on PAH concentrations were assessed with the indexes benzo[a]pyrene equivalent (BaPE) and lung cancer risk (LCR). In 2010, PM10 average concentration was higher in São Paulo than in the other two sites; 75 % of the samples presented concentrations above that recommended by World Health Organization. Levoglucosan/mannosan ratios for São Paulo samples suggested sugarcane burning; in 2010 it occurred in 70 % of São Paulo state municipalities. Vehicular related elements (Fe and Cu) also presented higher concentrations in São Paulo. As and Pb concentrations were higher in Medellín, attributed to industrial emissions. Ni was abundant in Lima atmosphere and associated to emissions from metal smelting facilities and ship heavy oil combustion. High BaPE and LCR were observed in most of the samples in São Paulo in the year of 2014, reaching critical values in the wintertime (above 1 ng m-3 and 10-4, respectively). Also, PAHs and biomass burning tracers concentrations were higher in this season. The vehicular tracer species were also more abundant in the intensive campaign (wintertime) suggesting the lower dispersion conditions, less rainfall and higher frequency of thermal inversions in that period. Positive matrix factorization provided a better comprehension over the contribution sources affecting the site; five different factors were identified: road dust, industrial emissions, vehicular exhaust, biomass burning and secondary formation. The results emphasized the contribution of vehicular emissions and the significant input from biomass combustion in the dry season (30,9 and 18,3 %, respectively). Most of the particulate matter was due to local sources (vehicular), besides the influence of pre-harvest sugarcane and urban biomass burning. Thus, the results emphasize the importance and contribution of the anthropogenic activities in the air quality for the three latin american cities.

Lai Ho-yan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves 104-122). / Abstracts in English and Chinese. / ACKNOWLEDGEMENT --- p.I / ABSTRACT (ENGLISH) --- p.II / ABSTRACT (CHINESE) --- p.IV / TABLE OF CONTENT --- p.VI / LIST OF FIGURES --- p.IX / LIST OF TABLES --- p.V / INTRODUCTION --- p.1 / Chapter 1.1 --- Background --- p.1 / Chapter 1.2 --- Sources of oil pollution --- p.1 / Chapter 1.3 --- Composition of oil --- p.4 / Chapter 1.4 --- Fate of oil in the environment --- p.6 / Chapter 1.5 --- Toxic effect of oil on marine ecosystem --- p.8 / Chapter 1.5.1 --- Acute toxicity --- p.8 / Chapter 1.5.2 --- Chronic toxicity --- p.9 / Chapter 1.5.3 --- Carcinogenicity of oil --- p.11 / Chapter 1.6 --- The origins of ecotoxicology --- p.12 / Chapter 1.7 --- Need for ecotoxicity tests --- p.13 / Chapter 1.8 --- Testings in ecotoxicology --- p.15 / OBJECTIVES --- p.17 / MATERIALS AND METHODS --- p.18 / Chapter 1. --- Collection of oily wastes samples --- p.18 / Chapter 2. --- Preparation of samples --- p.18 / Chapter 2.1 --- Water-soluble fraction --- p.19 / Chapter 2.2 --- Polycyclic aromatic hydrocarbon fraction --- p.20 / Chapter 2.2.1 --- Supercritical fluid extraction --- p.20 / Chapter 2.2.2 --- Silica gel chromatography --- p.22 / Chapter 2.2.3 --- Sample concentration --- p.22 / Chapter 3. --- Chemical analyses of oily wastes --- p.26 / Chapter 3.1 --- Determination of heavy metal concentration in oily waste samples --- p.26 / Chapter 3.1.1 --- Nitric acid-perchloric acid digestion --- p.26 / Chapter 3.1.2 --- Inductively coupled plasma-emission spectrometric analysis --- p.26 / Chapter 3.2 --- Determination of polycyclic aromatic hydrocarbon concentration in oily waste samples --- p.28 / Chapter 3.2.1 --- Determination of polycyclic aromatic hydrocarbon concentration in water- soluble fraction --- p.28 / Chapter a. --- Liquid-liquid extraction --- p.28 / Chapter b. --- Gas chromatography-mass spectrometric analysis of water-soluble fraction --- p.29 / Chapter 3.2.2 --- Determination of polycyclic aromatic hydrocarbon concentration in crude oily waste samples --- p.32 / Chapter a. --- Supercritical fluid extraction and silica gel column chromatography --- p.32 / Chapter b. --- Gas chromatography-mass spectrometric analysis of polycyclic aromatic hydrocarbon fraction --- p.33 / Chapter 4 --- ecotoxicological studies of oily wastes --- p.34 / Chapter 4.1 --- Toxicity tests and sample preparation --- p.34 / Chapter 4.2 --- Ecotoxicological studies of water soluble fraction --- p.34 / Chapter 4.2.1 --- "Growth inhibition test on a marine alga, Chlorella pyrenoidosa CU-2" --- p.34 / Chapter 4.2.2 --- "Survival test on a marine amphipod, Elasmopus rapax" --- p.39 / Chapter 4.2.3 --- "Survival test on a marine fish, Ambassis gymnocephalus" --- p.41 / Chapter 4.2.4 --- Microtox® test --- p.43 / Chapter 4.3. --- Ecotoxicological studies of polycyclic aromatic hydrocarbon fraction --- p.45 / Chapter 4.3.1 --- "Growth inhibition test on a marine alga, Chlorella pyrenoidosa CU-2" --- p.45 / Chapter 4.3.2 --- "Survival test on a amphipod, Parhyale plumulosa" --- p.45 / Chapter 4.3.3 --- "Survival test on the fish, Sparus sarba" --- p.47 / Chapter 4.3.4 --- Microtox® test --- p.49 / Chapter 5. --- Statistical analyses of chemical and ecotoxicological analyses --- p.50 / RESULTS --- p.51 / Chapter 1. --- Chemical analyses of oily wastes --- p.51 / Chapter 1.1 --- Inductively coupled plasma-emission spectrometric analysis --- p.51 / Chapter 1.1.1 --- Heavy metal concentration in crude oily wastes --- p.51 / Chapter 1.1.2 --- Heavy metal concentration in water-soluble fraction --- p.51 / Chapter 1.1.3 --- Heavy metal concentration in ploy cyclic aromatic hydrocarbon fraction --- p.54 / Chapter 1.2 --- Gas chromatography- mass spectrometry analysis --- p.54 / Chapter 1.2.1 --- Polycyclic aromatic hydrocarbon concentration in crude oily wastes --- p.54 / Chapter 1.2.2 --- Polycyclic aromatic hydrocarbons concentration in water-soluble fraction --- p.59 / Chapter 1.2.3 --- Polycyclic aromatic hydrocarbons concentration in polycyclic aromatic hydrocarbon fraction --- p.61 / Chapter 2. --- Ecotoxicological studies of oily wastes --- p.63 / Chapter 2.1 --- Ecotoxicological studies of water-souble fraction --- p.63 / Chapter 2.1.1 --- Growth inhibition test on Chlorella pyrenoidosa CU-2 --- p.63 / Chapter 2.1.2 --- Survival test on Elasmopous rapax --- p.63 / Chapter 2.1.3 --- Survival test on Ambassis gymnocephalus --- p.67 / Chapter 2.1.4 --- Microtox® test --- p.67 / Chapter 2.2 --- Ecotoxicological studies of polycyclic aromatic hydrocarbon fraction --- p.70 / Chapter 2.2.1 --- Growth inhibition test on Chlorella pyrenoidosa CU-2 --- p.70 / Chapter 2.2.2 --- Survival test on Parhyale plumulosa --- p.70 / Chapter 2.2.3 --- Survival test on Sparus sarba --- p.74 / Chapter 2.2.4 --- Microtox® test --- p.74 / Chapter 3. --- Statistical analyses of chemical and ecotoxicological studies --- p.77 / Chapter 3.1 --- Statistical analyses of studies on water-soluble fraction --- p.77 / Chapter 3.1.1 --- Correlation between heavy metal concentration in water-soluble fraction and toxicity tests --- p.77 / Chapter 3.1.2 --- Correlation between concentration of total polycyclic aromatic hydrocarbon in water-soluble fraction and toxicity tests --- p.80 / Chapter 3.1.3 --- Correlation among acute toxicity tests --- p.80 / Chapter 3.2 --- Statistical analyses of polycyclic aromatic hydrocarbon fraction --- p.84 / Chapter 3.2.1 --- Correlation between heavy metal level and toxicity tests --- p.84 / Chapter 3.2.2 --- Correlation between total polycyclic aromatic hydrocarbon concentration in polycyclic aromatic hydrocarbon fraction and toxicity tests --- p.84 / Chapter 3.2.3 --- Correlation between four acute toxicity tests --- p.88 / DISCUSSION --- p.91 / Chapter 1 --- Chemical analyses of oily wastes --- p.91 / Chapter 1.1 --- Inductively coupled plasma-emission spectrometric analysis --- p.91 / Chapter 1.2 --- Gas chromatography-mass spectrometry analysis --- p.93 / Chapter 2. --- ecotoxicological studies of oily wastes --- p.95 / Chapter 2.1 --- Growth inhibition test on Chlorella pyrenoidosa CU-2 --- p.95 / Chapter 2.2 --- Survival tests on Elasmopus rapax and Parhyale plumulosa --- p.96 / Chapter 2.3 --- Survival test on Ambassis gymnocephalus and Sparus sarba --- p.97 / Chapter 2.4 --- Microtox® test --- p.98 / Chapter 3 --- Statistical analyses of chemical and ecotoxicological analyses --- p.99 / Chapter 4. --- statistical analyses between acute toxicity tests --- p.101 / CONCLUSION --- p.102 / REFERENCES --- p.104

Os hidrocarbonetos policíclicos aromáticos (HPAs) são uma classe de substâncias químicas que podem ser geradas na combustão de matéria orgânica, e 17 destas substâncias são consideradas como poluentes prioritários pela Agência de Proteção Ambiental dos EUA (US EPA), em função de seu potencial tóxico e carcinogênico. Para identificar e quantificar os HPAs no ambiente de trabalho por cromatografia gasosa / espectrometria de massas, foram realizadas coletas de amostras ambientais em um incinerador de resíduos de serviços de saúde localizado na região da grande São Paulo e em três fundições de metais nas cidades de Loanda e Santa Isabel do Ivaí, no Estado do Paraná. A concentração de HPAs totais nas amostras ambientais coletadas no Incinerador foi de 0,36 - 1,72 &#181;g/m3; na Fundição 1 de 0,72 - 4,56 &#181;g/m3; na Fundição 2 de 2,32 - 6,52 &#181;g/m3; na Fundição 3 de 0,19 - 3,72 &#181;g/m3. Foi realizada também a coleta de amostras biológicas de trabalhadores expostos e não expostos, para a identificação e quantificação do indicador biológico de exposição o 1-hidroxipireno por cromatografia líquida com detector de fluorescência. A concentração de 1-hidroxipireno nas amostrados biológicas dos trabalhadores no Incinerador apresentou diferença estatisticamente siginificante entre o grupo exposto e o grupo controle; na Fundição 1 houve diferença estatisticamente pouco significante entre os grupos estudados; nas Fundições 2 e 3 não houve diferença estatisticamente significante entre os grupos estudados. / The Polycyclic Aromatics Hydrocarbons (PAH) are a class of chemicals that can to be generated by organic matter burning, and 17 of that chemicals are considered priority pollutant by Environmental Protection Agency (US EPA), because their toxicity and carcinogenicity potentials. To identify and to quantitify the PAH at workplace atmosphere by gas chromatography/mass spectrometry (GC/MS), it was conducted a environmental sampling in a waste incinerator, settled in the metropolitan São Paulo Region, and at three metals foundry settled in the Loanda City and Santa Isabel do Ivaí City, at Paraná State. The concentration of total PAH in the environmental samples collected in a waste incinerator was 0,36 - 1,72 &#181;g/m3; at metals foundry 1 was 0,72 - 4,56 &#181;g/m3; at metals foundry 2 was 2,32 - 6,52 &#181;g/m3; at metals foundry 3 was 0,19 - 3,72 &#181;g/m3. The biological samples of the workers was collected to identify and to quantitify the biological indicator urinary 1-hydroxypyrene (1-OH-Pyr) by high performance liquid chromatography/fluorescence detector (HPLC-Flu). The 1-OH-Pyr concentration in the biological samples of the exposed and control group in a waste incinerator presented a statistical significant difference; in the metals foundry 1 was observed a slight statistical significant difference; and in the metals foundry 2 and metals foundry 3 was not observed statistical significant difference.