Ο Πατραϊκός Κόλπος βρίσκεται στη Δυτική Ελλάδα μεταξύ Στερεάς Ελλάδας και Πελοποννήσου. Είναι ένας σχετικά αβαθής θαλάσσιος κόλπος που συνδέει το βαθύ Κορινθιακό Κόλπο με το Ιόνιο Πέλαγος. Η περιοχή μελέτης εκτείνεται από την παραλία της Καλόγριας, Δ. Λαρισσού, μέχρι το Ακταίο του Δήμου Ρίου. Πραγματοποιηθήκαν 2 εποχικές δειγματοληψίες, για τη συλλογή θαλάσσιου νερού, μια χειμερινή το Μάρτιο του 2009 και μία θερινή το Σεπτέμβριο του ίδιου έτους. Εμβόλιμα έγινε δειγματοληψία λίγο μετά από ατύχημα πετρελαιοκηλίδας στο λιμάνι της Πάτρας. Στην εργασία αυτή με μία τροποποίηση της μεθόδου MARPOLMON-P, μετρήθηκε η εκπομπή φθορισμού των δειγμάτων μετά από την εκχύλιση τους με εξάνιο και διερευνήθηκε η παρουσία και η συγκέντρωση πετρελαϊκών ενώσεων καθώς και η διασπορά των πετρελαιοειδών στις παράκτιες περιοχές του Πατραϊκού Κόλπου. Σε κάθε δείγμα μετρήθηκαν φυσικές παράμετροι όπως η θερμοκρασία, το pH, η ηλεκτρική αγωγιμότητα και η θολερότητα του θαλάσσιου νερού. Η σύσταση των δειγμάτων της δεύτερης δειγματοληψίας διερευνήθηκε με τη χρήση GC-MS για τον εντοπισμό της πηγής των πετρελαϊκών ρύπων. Τα αποτελέσματα των δύο κύριων δειγματοληψιών παρουσίασαν μεγάλες διακυμάνσεις στη συγκέντρωση αλλά και στην κατανομή των πετρελαϊκών υδρογονανθράκων, με τα εύρη των τιμών των συγκεντρώσεων να κυμαίνονται για τη χειμερινή από 0 – 290 μg/L ισοδύναμων μονάδων χρυσενίου (Λιμάνι Προβλήτα Αγ. Νικολάου) και για τη θερινή δειγματοληψία από 0- 56 μg/L μονάδων χρυσενίου (Μαρίνα Τερψιθέας). Η κατανομή και η διασπορά των πετρελαιοειδών φαίνεται να επηρεάζεται άμεσα από τη διεύθυνση και ταχύτητα των κυμάτων και του επικρατούντος άνεμου στις περιοχές δειγματοληψίας, αλλά και από την ωκεανογραφική συμπεριφορά του Πατραϊκού Κόλπου. Στην ανάλυση GC/MS βρέθηκε μεγάλη αναλογία αλκάνιων σε όλα τα δείγματα, ενώ σε κάποια από αυτά βρέθηκαν πολυκυκλικοί αρωματικοί υδρογονάνθρακες και αλκένια, παράγωγα του πετρελαίου και των καυσίμων. Άλλες οργανικές ενώσεις όπως φθαλικοί εστέρες, σουλφίδια, αλκοόλες κ.α., ανιχνεύτηκαν σε χαμηλές συνήθως συγκεντρώσεις και πιθανόν προέρχονται από ρυπογόνες χερσαίες πηγές (επιφανειακή απορροή, αστικά και βιομηχανικά λύματα κ.α.). / The Gulf of Patras located between Continental Greece and Peloponnesus, in West Greece. The Gulf of Patras is relatively shallow and connects the deep Gulf of Corinth with Ionian Open Sea. The experimental area of our study extends from the beach of Kalogria, department of Municipality of Larissos, to Aktaion, department of Municipality of Rion. Two samplings, one in March of 2009 and one in September of the same year, were carried out in order to get sea water samples. After the occurrence of an oil slick accident in the port of Patras, an interstitial sampling was carried out. In this study, MARPOLMON-P method partially modified was used, in order to estimate the fluorescence emission of the hexane extracted sea water samples. The presence of Dissolved/Dispersed petroleum hydrocarbons (DDPH) was also investigated as well as their concentration and the distribution of those in the maritime areas of the Gulf of Patras. In every sample, physical parameters such as temperature, pH, electrical conductivity and turbidity of sea water were estimated. The identification of various substances within the samples of the second sampling (September of 2009) was conducted with GC-MS method, in order to find out the source of oil pollution. Considering our results of the two main samplings we found out that there were important ranges in concentration as well as in distribution of DDPH. At first sampling the range of values was between 0 to 290 μg/L of chrysene equivalents (Port of St. Nikolaos) and at second sampling was between 0 to 56 μg/L of chrysene equivalents (Port of Marina Terpsithea). The results showed that wave’s direction and speed, wind speed and oceanographical status of Gulf of Patras affected by the distribution and dispersion of petroleum hydrocarbons. During the GC/MS analysis high content of alkanes in all collected samples was identified, while some of them contained polycyclic aromatic hydrocarbons and alkenes, such as products of crude oil and mineral fuel. Other organic compounds such as pthallic esters, sulphides, alcoholes etc were found in low concentrations. These organic compounds were probably derived from pollutant ground sources (superficial rain flow or dilution drainage, urban and manufacturing wastesreams).

[pt] Esta dissertação apresenta os resultados de duas técnicas de investigação em alta resolução: investigação passiva de vapores do solo e investigação com o uso de Membrane Interface Probe (MIP), em uma área de interesse com contaminação por hidrocarbonetos, localizada no município de Duque de Caxias/RJ. O processo de gerenciamento ambiental iniciou-se em 2012 na área e contemplou as etapas do gerenciamento de áreas contaminadas preconizadas nas legislações vigentes. Os resultados obtidos a partir das investigações tradicionais foram insuficientes para a obtenção da compreensão dos aspectos físicos e geoquímicos necessária para o sucesso das fases de diagnóstico e, consequentemente, da remediação. Portanto, duas investigações em alta resolução foram conduzidas com o objetivo de refinar o modelo conceitual de forma a atender adequadamente a Resolução CONAMA número 420/09 e Resolução CONEMA número 44/12, permitindo ações futuras mais eficientes. A investigação passiva de vapores do solo utilizou amostradores compostos por materiais adsorventes granulares, encapsulados em uma membrana microporosa hidrofóbica e quimicamente inerte que permite a difusão dos vapores presentes no meio. Os resultados, fornecidos em massa, representam qualitativamente a presença de contaminação no subsolo. O MIP é uma ferramenta de direct push com medição em tempo real, que mapeia a presença da contaminação tanto em meios insaturados quanto saturados inconsolidados. A partir dos resultados integrados, foi possível constatar que a distribuição de VOCs em água subterrânea ocorre de forma descontínua ao longo da área, sendo possível identificar cinco hot-spots distintos e suas diferentes áreas fonte, incluindo uma região com presença de LNAPL. / [en] The sources of contaminated sites are related to several factors such as the lack of knowledge of safe procedures for handling hazardous and / or toxic substances, disrespect to these safe procedures and the occurrence of accidents or leaks during industrial processes, transportation or storage of unprocessed materials and products. In addition, contamination is usually associated with the exploration of natural resources and with the expansion of the industry and/or agrarian activities, which have happened, and are still happening, at the cost of high environmental and social risks. A contaminated site is considered a risk, since its existence can generate several problems such as damages to health, impairment of the quality of water resources, restrictions on land use and damage to public and private property, and damage to the environment. These situations, in general, involve complex risks with regard to the effects of exposure to contaminants on human health (CETESB, 2013), and may have short -, medium - or long-term effects.

Orientador: Rodrigo Sequinel / Coorientador: Danilo Luiz Flumignan / Banca: Edilene Cristina Ferreira / Banca: Erica Regina Filletti Nascimento / Banca: Mária Cristina Breitkreitz / Banca: Heron Dominguez Torres da Silva / Resumo: Segundo dados, de 2017, da Companhia Ambiental do Estado de São Paulo (CETESB), os postos de combustíveis são responsáveis pela contaminação ambiental de 72% das 5942 áreas contaminadas cadastradas no estado de São Paulo. A contaminação de solos e águas subterrâneas por combustíveis fósseis causam imensos danos ambientais devido à alta toxicidade dos constituintes destes combustíveis, além de apresentarem propriedades carcinogênicas e elevada permanência no solo. O monitoramento ambiental em áreas de risco potencial de contaminação, como postos de combustíveis, é realizado através da análise de hidrocarbonetos totais do petróleo (TPH), entre outros hidrocarbonetos individuais. Estas análises são realizadas através de métodos cromatográficos em fase gasosa que requerem etapas de extração com solventes halogenados, purificação e, muitas vezes, pré-concentração. O elevado custo e o tempo demandado para a quantificação de TPH em solo tornam-se barreiras para o crescimento do monitoramento e acompanhamento de processos de remediação das áreas contaminadas. Desta forma, este trabalho objetivou o desenvolvimento de métodos analíticos mais rápidos e de menor custo para a identificação e quantificação de TPH em solo através da espectroscopia na região do infravermelho próximo (NIR). Três métodos NIR foram desenvolvidos: (i) sem preparo de amostra; (ii) após extração por hexano; e (iii) após extração por etanol. Os modelos de classificação foram desenvolvidos pelo método de análise dis... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: According to the Environmental Company of the State of São Paulo (CETESB), the gas stations are responsible for the environmental contamination of 72% of the 5942 contaminated areas registered in the state of São Paulo. Contamination of soils and groundwater by fossil fuels causes immense environmental damages due to their high toxicity, carcinogenic properties and high permanence in the soil. Environmental monitoring in areas of potential contamination risk, such as gas stations, is carried out through the analysis of total petroleum hydrocarbons (TPH), among other individual compounds. These analyzes are performed by gas chromatographic methods which require some sample preparation steps, such as extraction with halogenated solvents, purification, and often preconcentration. The high cost and time demanded for the quantification of TPH in the soil become barriers for the growth of the monitoring program and remediation processes of the contaminated areas. Therefore, this work aimed at the development of faster and lower cost analytical methods for the identification and quantification of TPH in soil through near-infrared spectroscopy (NIR). Three NIR methods were developed: (i) without sample preparation; (ii) after hexane extraction; and (iii) after extraction with ethanol. The classification models were developed by partial least squares discriminant analysis (PLS-DA) method and the calibration models by partial least squares (PLS) method. In the development of the models... (Complete abstract click electronic access below) / Doutor

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O presente trabalho teve por objetivo apresentar e discutir um caso de identificação e remediação emergencial de compostos orgânicos voláteis, oclusos em camada arenosa do Terciário da Formação São Paulo, em decorrência do vazamento de tanques de combustíveis de um posto de serviços. A técnica de remediação adotada para o caso consistiu na extração in situ dos vapores do solo e no tratamento dos mesmos por adsorção em filtros de carvão ativado (SVE - soil vapor extraction). Os processos de seleção, projeto, implantação, operação e descomissionamento da tecnologia SVE seguiram as metodologias indicadas pela literatura, adaptadas às condições locais. O acompanhamento da eficiência da remediação foi baseado na quantificação inicial dos hidrocarbonetos totais de petróleo leves presentes no subsolo, através das técnicas de cromatografia gasosa e espectrometria de massa, e na medição em campo das concentrações de voláteis e dos respectivos teores de explosividade. O resultado da campanha laboratorial apresentou fortes indícios de que a contaminação local fosse proveniente do combustível gasolina e indicou a ocorrência do composto benzeno em concentrações superiores aos limites adotados como referência. As leituras realizadas em campo mostraram rápido declínio das concentrações de voláteis e dos teores de explosividade com a operação da tecnologia SVE, indicando baixa ocorrência de fatores limitantes do transporte de massa no local. Corroborou com tal hipótese, o fato das metas de remediação terem sido atingidas com poucas trocas de ar, parâmetro retro-analisado a partir de dados de ensaios geológico-geotécnicos. Assim, concluiu-se que, para áreas com características semelhantes à estudada, a tecnologia SVE pode ser eficiente como medida de remediação de voláteis e redução dos riscos de explosividade. / This work aims to present and to discuss a case study of identification and emergency remediation of volatile organic compounds, occluded in a sand layer of the São Paulo Tertiary Formation, as a result of the leakage of fuel tanks of a service station. The adopted remediation technique was in situ soil vapor extraction (SVE) and offgas treatment for adsorption in activated carbon filters. Selection, design, commissioning, operation and shutdown processes of SVE technology followed literature methodologies, which were adapted to local conditions. Remediation efficiency monitoring was based on the initial quantification of light total petroleum hydrocarbons in the subsoil, through gas chromatography and mass spectrometry techniques, and on measurement of the volatile concentrations and respective explosive contents in the field. The result of the laboratorial campaign presented strong indications that the local contamination proceeded from combustible gasoline and it indicated the occurrence of benzene in concentrations higher than the adopted reference. Field measurements showed fast decline of the volatile concentrations and explosive contents with the SVE technology operation, fact that indicated low occurrence of mass transfer limitations in the place. The fact that remediation goals were achieved with few air exchanges, parameter back-analyzed from geologicgeotechnical tests, contributed to reinforce such hypothesis. Thus, SVE technique can be considered efficient for volatile remediation and explosive risks reduction, for areas with characteristics similar to the studied one.

O presente trabalho teve por objetivo apresentar e discutir um caso de identificação e remediação emergencial de compostos orgânicos voláteis, oclusos em camada arenosa do Terciário da Formação São Paulo, em decorrência do vazamento de tanques de combustíveis de um posto de serviços. A técnica de remediação adotada para o caso consistiu na extração in situ dos vapores do solo e no tratamento dos mesmos por adsorção em filtros de carvão ativado (SVE - soil vapor extraction). Os processos de seleção, projeto, implantação, operação e descomissionamento da tecnologia SVE seguiram as metodologias indicadas pela literatura, adaptadas às condições locais. O acompanhamento da eficiência da remediação foi baseado na quantificação inicial dos hidrocarbonetos totais de petróleo leves presentes no subsolo, através das técnicas de cromatografia gasosa e espectrometria de massa, e na medição em campo das concentrações de voláteis e dos respectivos teores de explosividade. O resultado da campanha laboratorial apresentou fortes indícios de que a contaminação local fosse proveniente do combustível gasolina e indicou a ocorrência do composto benzeno em concentrações superiores aos limites adotados como referência. As leituras realizadas em campo mostraram rápido declínio das concentrações de voláteis e dos teores de explosividade com a operação da tecnologia SVE, indicando baixa ocorrência de fatores limitantes do transporte de massa no local. Corroborou com tal hipótese, o fato das metas de remediação terem sido atingidas com poucas trocas de ar, parâmetro retro-analisado a partir de dados de ensaios geológico-geotécnicos. Assim, concluiu-se que, para áreas com características semelhantes à estudada, a tecnologia SVE pode ser eficiente como medida de remediação de voláteis e redução dos riscos de explosividade. / This work aims to present and to discuss a case study of identification and emergency remediation of volatile organic compounds, occluded in a sand layer of the São Paulo Tertiary Formation, as a result of the leakage of fuel tanks of a service station. The adopted remediation technique was in situ soil vapor extraction (SVE) and offgas treatment for adsorption in activated carbon filters. Selection, design, commissioning, operation and shutdown processes of SVE technology followed literature methodologies, which were adapted to local conditions. Remediation efficiency monitoring was based on the initial quantification of light total petroleum hydrocarbons in the subsoil, through gas chromatography and mass spectrometry techniques, and on measurement of the volatile concentrations and respective explosive contents in the field. The result of the laboratorial campaign presented strong indications that the local contamination proceeded from combustible gasoline and it indicated the occurrence of benzene in concentrations higher than the adopted reference. Field measurements showed fast decline of the volatile concentrations and explosive contents with the SVE technology operation, fact that indicated low occurrence of mass transfer limitations in the place. The fact that remediation goals were achieved with few air exchanges, parameter back-analyzed from geologicgeotechnical tests, contributed to reinforce such hypothesis. Thus, SVE technique can be considered efficient for volatile remediation and explosive risks reduction, for areas with characteristics similar to the studied one.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-10-15T23:53:48Z No. of bitstreams: 1 ADNA DE ALCÂNTARA E SOUZA BANDEIRA - DISSERTAÇÃO PPGEQ 2010..pdf: 10337833 bytes, checksum: 8e5aa72a95f83ae8223a787549af0b73 (MD5) / Made available in DSpace on 2018-10-15T23:53:48Z (GMT). No. of bitstreams: 1 ADNA DE ALCÂNTARA E SOUZA BANDEIRA - DISSERTAÇÃO PPGEQ 2010..pdf: 10337833 bytes, checksum: 8e5aa72a95f83ae8223a787549af0b73 (MD5) Previous issue date: 2010-11-30 / A indústria petrolífera tem se desenvolvido muito rapidamente nos últimos anos devido aos avanços na descoberta e perfuração de poços cada vez mais profundos. Os resíduos dessas indústrias são classificados pela Associação Brasileira de Normas Técnicas ABNT (2004) como perigosos (Classe I). A Estabilização por Solidificação tem se mostrado uma tecnologia eficiente e bastante utilizada para atenuar e tratar resíduos perigosos além realizar o pré-tratamento dos resíduos antes da disposição em aterro industrial. O objetivo principal desse trabalho foi atenuar Hidrocarbonetos Totais de Petróleo e Óleos e Graxas presentes na borra oleosa de petróleo usando Estabilização por Solidificação. Este trabalho foi realizado no Laboratório de Gestão Ambiental e Tratamento de Resíduos que pertence à Unidade Acadêmica de Engenharia Química da Universidade Federal de Campina Grande. Foi dividido em quatro etapas. Na primeira etapa foi realizado o planejamento experimental. Foi utilizado o fatorial 22 com três pontos centrais. Os fatores adotados foram percentual de borra (10, 15 e 20%) e temperatura de cura (0, 20 e 40°C). Na segunda etapa foi feita a caracterização e classificação da borra de petróleo. Na terceira etapa foi realizada a avaliação dos materiais submetidos à estabilização por solidificação, utilizando uma mistura de cimento Portland simples e argila organofílica como aglomerantes, usando critérios de integridade/durabilidade e imobilização dos contaminantes. Na quarta etapa foi realizada a análise estatística e o balanço de massa do processo. Com esse trabalho, foi possível verificar que a capacidade de absorção de água nos corpos de prova influencia na sua resistência à compressão e, posteriormente, na lixiviação. O teor de óleos e graxas na borra de petróleo é um indicativo de contaminação. Com o tratamento, conseguiu-se uma redução de 86,7% no teor de óleos e graxas, mostrando que a Estabilização por Solidificação pode ser aplicada como pré-tratamento de resíduos perigosos antes de serem dispostos adequadamente em aterros sanitários industriais e/ou como forma de efetuar a atenuação dos contaminantes. Observou-se também que a temperatura não influenciou no processo e que apenas a percentagem de borra pode influenciar nos resultados de óleos e graxas. / The oil industry has developed very rapidly in recent years due to advances in the discovery and drilling wells deeper and deeper. Waste is classified by the Brazilian Association of Technical Standards (ABNT, 2004) as hazardous (Class I). The stabilization by solidification technology has proved an effective and widely used to alleviate and treat hazardous waste in addition carry out pre-treat waste before disposal in landfill. The main objective of this study was to soften Total Petroleum Hydrocarbons and oils/greases present in oily sludge using oil stabilization by solidification. This work was performed at the Laboratory of Environmental Management and Waste belonging to the Academic Department of Chemical Engineering, Federal University of Campina Grande. It was divided into four stages. In the first stage we carried out the experimental design. We used the 2 factorial with three central points. The factors used were the percentage of sludge (10, 15 and 20%) and curing temperature (0, 20 and 40 0 C). The second step was the characterization and classification of oil sludge. The third step was performed to evaluate the materials submitted to the stabilization by solidification using a simple mixture of Portland cement and organoclay as binders, using criteria of integrity/durability and immobilization of contaminants. The fourth stage was performed statistical analysis and mass balance of the process. With this work, we observed that the capacity of water absorption in the specimens influences the compressive strength and the later leaching. The content of oils and greases in the oil sludge is an indicator of contamination. With treatment, achieved a reduction of 86.7% in the concentration of oils and greases, showing that the stabilization by solidification can be applied as a pretreatment of hazardous waste before being appropriately disposed of in landfills and industrial and/or as how to make the attenuation of contaminants. We also observed that the temperature did not influence the process and that only the percentage of sludge can influence the results of oils and greases.

Submitted by Maurilio Gustavo Nespeca (mauriliogn@hotmail.com) on 2018-08-31T21:01:07Z No. of bitstreams: 1 TESE - MAURILIO G NESPECA.pdf: 12338235 bytes, checksum: 0ffb2ce70bfeb2d88ea11b6f84d923e9 (MD5) / Approved for entry into archive by Ana Carolina Gonçalves Bet null (abet@iq.unesp.br) on 2018-09-04T12:54:22Z (GMT) No. of bitstreams: 1 nespeca_mg_dr_araiq_int.pdf: 8911620 bytes, checksum: d6033930d5b3d08e08ac463efd5ad737 (MD5) / Made available in DSpace on 2018-09-04T12:54:22Z (GMT). No. of bitstreams: 1 nespeca_mg_dr_araiq_int.pdf: 8911620 bytes, checksum: d6033930d5b3d08e08ac463efd5ad737 (MD5) Previous issue date: 2018-08-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Segundo dados, de 2017, da Companhia Ambiental do Estado de São Paulo (CETESB), os postos de combustíveis são responsáveis pela contaminação ambiental de 72% das 5942 áreas contaminadas cadastradas no estado de São Paulo. A contaminação de solos e águas subterrâneas por combustíveis fósseis causam imensos danos ambientais devido à alta toxicidade dos constituintes destes combustíveis, além de apresentarem propriedades carcinogênicas e elevada permanência no solo. O monitoramento ambiental em áreas de risco potencial de contaminação, como postos de combustíveis, é realizado através da análise de hidrocarbonetos totais do petróleo (TPH), entre outros hidrocarbonetos individuais. Estas análises são realizadas através de métodos cromatográficos em fase gasosa que requerem etapas de extração com solventes halogenados, purificação e, muitas vezes, pré-concentração. O elevado custo e o tempo demandado para a quantificação de TPH em solo tornam-se barreiras para o crescimento do monitoramento e acompanhamento de processos de remediação das áreas contaminadas. Desta forma, este trabalho objetivou o desenvolvimento de métodos analíticos mais rápidos e de menor custo para a identificação e quantificação de TPH em solo através da espectroscopia na região do infravermelho próximo (NIR). Três métodos NIR foram desenvolvidos: (i) sem preparo de amostra; (ii) após extração por hexano; e (iii) após extração por etanol. Os modelos de classificação foram desenvolvidos pelo método de análise discriminante por mínimos quadrados parciais (PLS-DA) e os modelos de calibração por mínimos quadrados parciais (PLS). No desenvolvimento dos modelos, nove diferentes pré-processamentos e seleção de variáveis pelo algoritmo genético (GA) foram avaliados. Os modelos foram desenvolvidos usando-se amostras de solo fortificado com os contaminantes (gasolina, diesel e óleo lubrificantes) e validados com amostras de solo contaminado, adquiridas no monitoramento ambiental de postos de combustíveis. O modelo PLS-DA proporcionou 100% de classificações corretas das amostras contaminadas sem a necessidade de preparo de amostra, enquanto a predição da concentração dos analitos tornou-se possível através dos modelos PLS após a etapa de extração com etanol. Como objetivos secundários deste trabalho, foram desenvolvidos métodos de quantificação das diferentes frações de TPH e dos compostos benzeno, tolueno, etilbenzeno e xilenos (BTEX) por cromatografia em fase gasosa ultrarrápida com detector de ionização por chama (UFGC-FID). Além do desenvolvimento dos métodos UFGC-FID, otimizou-se o processo de extração dos analitos por sonicação através de planejamentos experimentais, avaliando-se diferentes solventes, tempo de sonicação, agitação por vórtex e volume de solvente. Os métodos UFGC-FID proporcionaram análises de 3 a 17 vezes mais rápidas que o método cromatográfico de acordo com a norma EPA 8015. Ao final deste trabalho, os métodos desenvolvidos e o método EPA 8015 foram comparados segundo aspectos analíticos, ambientais e financeiros. De forma geral, os três métodos apresentaram mesma exatidão; o método cromatográfico (EPA 8015) foi o método mais preciso; o método UFGC-FID foi o de menor investimento inicial e de menor tempo para retorno financeiro; e, finalmente, o método NIR após extração com etanol foi o mais sensível, rápido, favorável à química verde e de menor custo por análise. / According to the Environmental Company of the State of São Paulo (CETESB), the gas stations are responsible for the environmental contamination of 72% of the 5942 contaminated areas registered in the state of São Paulo. Contamination of soils and groundwater by fossil fuels causes immense environmental damages due to their high toxicity, carcinogenic properties and high permanence in the soil. Environmental monitoring in areas of potential contamination risk, such as gas stations, is carried out through the analysis of total petroleum hydrocarbons (TPH), among other individual compounds. These analyzes are performed by gas chromatographic methods which require some sample preparation steps, such as extraction with halogenated solvents, purification, and often preconcentration. The high cost and time demanded for the quantification of TPH in the soil become barriers for the growth of the monitoring program and remediation processes of the contaminated areas. Therefore, this work aimed at the development of faster and lower cost analytical methods for the identification and quantification of TPH in soil through near-infrared spectroscopy (NIR). Three NIR methods were developed: (i) without sample preparation; (ii) after hexane extraction; and (iii) after extraction with ethanol. The classification models were developed by partial least squares discriminant analysis (PLS-DA) method and the calibration models by partial least squares (PLS) method. In the development of the models, we evaluated nine different preprocessing and selection of variables by the genetic algorithm (GA). The models were developed using soil samples fortified with contaminants (gasoline, diesel and lubricant oil) and validated with samples of contaminated soil acquired in the environmental monitoring of gas stations. The PLS-DA model provided 100% correct classifications without sample preparation, while the prediction of the concentration of the analytes was possible by PLS models after the ethanol extraction. As secondary objectives of this work, we developed quantification methods for the different fractions of TPH and benzene, toluene, ethylbenzene, and xylenes (BTEX) compounds by ultrafast gas chromatography with flame ionization detector (UFGC-FID). In addition to the UFGC-FID methods, the TPH extraction by sonication was optimized through experimental design, evaluating different solvents, sonication time, agitation and solvent volume. The UFGC-FID methods provided analyzes 3 to 17 times faster than the chromatographic method according to EPA 8015. At the end of this work, the developed methods and the EPA 8015 method were compared according to analytical, environmental and financial aspects. In general, the three methods presented the same accuracy; the EPA 8015 method was the most precise; the UFGC-FID method presented lower initial investment and less time for financial return; and the NIR method after ethanol extraction was the most sensitive, fast, favorable to green chemistry and presented the lowest cost per analysis.

Les champignons mycorhiziens à arbuscules (CMA) forment un groupe de champignons qui appartient à l'embranchement des Gloméromycètes (Glomeromycota). Les CMA forment des associations symbiotiques, connus sous le nom des mycorhizes à arbuscules avec plus de 80 % des plantes vasculaires terrestres. Une fois que les CMA colonisent les racines de plantes, ils améliorent leurs apports nutritionnels, notamment le phosphore et l'azote, et protègent les plantes contre les différents pathogènes du sol. En contrepartie, les plantes offrent un habitat et les ressources de carbone nécessaires pour le développement et la reproduction des CMA. Des études plus récentes ont démontré que les CMA peuvent aussi jouer des rôles clés dans la phytoremédiation des sols contaminés par les hydrocarbures pétroliers (HP) et les éléments traces métaliques. Toutefois, dans les écosystèmes naturels, les CMA établissent des associations tripartites avec les plantes hôtes et les microorganismes (bactéries et champignons) qui vivent dans la rhizosphère, l'endosphère (à l'intérieur des racines) et la mycosphère (sur la surface des mycéliums des CMA), dont certains d'entre eux jouent un rôle dans la translocation, l’immobilisation et/ou la dégradation des polluants organiques et inorganiques présents dans le sol. Par conséquent, la diversité des CMA et celle des microorganismes qui leur sont associés sont influencées par la concentration et la composition des polluants présents dans le sol, et aussi par les différents exsudats sécrétés par les trois partenaires (CMA, bactéries et les racines de plantes). Cependant, la diversité des CMA et celle des microorganismes qui leur sont associés demeure très peu connue dans les sols contaminés. Les interactions entre les CMA et ces microorganismes sont aussi méconnus aussi bien dans les aires naturelles que contaminées. Dans ce contexte, les objectifs de ma thèse sont: i) étudier la diversité des CMA et les microorganismes qui leur sont associés dans des sols contaminés par les HP, ii) étudier la variation de la diversité des CMA ainsi que celle des microorganismes qui leur sont associés par rapport au niveau de concentration en HP et aux espèces de plantes hôtes, iii) étudier les correlations (covariations) entre les CMA et les microorganismes qui leur sont associés et iv) comparer les communautés microbiennes trouvées dans les racines et sols contaminés par les HP avec celles trouvées en association avec les CMA. Pour ce faire, des spores et/ou des propagules de CMA ont été extraites à partir des racines et des sols de l'environnement racinaire de trois espèces de plantes qui poussaient spontanément dans trois bassins de décantation d'une ancienne raffinerie de pétrole située dans la Rive-Sud du fleuve St-Laurent, près de Montréal. Les spores et les propagules collectées, ainsi que des échantillons du sol et des racines ont été soumis à des techniques de PCR (nous avons ciblés les genes 16S de l'ARNr pour bactéries, les genes 18S de l'ARNr pour CMA et les régions ITS pour les autres champignons), de clonage, de séquençage de Sanger ou de séquençage à haut débit. Ensuite, des analyses bio-informatiques et statistiques ont été réalisées afin d'évaluer les effets des paramètres biotiques et abiotiques sur les communautés des CMA et les microorganismes qui leur sont associés. Mes résultats ont montré une diversité importante de bactéries et de champignons en association avec les spores et les propagules des CMA. De plus, la communauté microbienne associée aux spores des CMA a été significativement affectée par l'affiliation taxonomique des plantes hôtes et les niveaux de concentration en HP. D'autre part, les corrélations positives ou négatives qui ont été observées entre certaines espèces de CMA et microorganismes suggérèrent qu’en plus des effets de la concentration en HP et l'identité des plantes hôtes, les CMA peuvent aussi affecter la structure des communautés microbiennes qui vivent sur leurs spores et mycéliums. La comparaison entre les communautés microbiennes identifiées en association avec les spores et celles identifiées dans les racines montre que les communautés microbiennes recrutées par les CMA sont différentes de celles retrouvées dans les sols et les racines. En conclusion, mon projet de doctorat apporte de nouvelles connaissances importantes sur la diversité des CMA dans un environnement extrêmement pollué par les HP, et démontre que les interactions entre les CMA et les microorganismes qui leur sont associés sont plus compliquées que ce qu’on croyait précédemment. Par conséquent, d'autres travaux de recherche sont recommandés, dans le futur, afin de comprendre les processus de recrutement des microorganismes par les CMA dans les différents environnements. / Arbuscular mycorrhizal fungi (AMF) are an important soil fungal group that belongs to the phylum Glomeromycota. AMF form symbiosic associations known as arbuscular mycorrhiza with more than 80% of vascular plants on earth. Once AMF colonize plant roots, they promote nutrient uptake, in particular phosphorus and nitrogen, and protect plants against soil-borne pathogens. In turn, plants provide AMF with carbon resources and habitat. Furthermore, more recent studies demonstrated that AMF may also play key roles in phytoremediation of soils contaminated with petroleum hydrocarbon pollutants (PHP) and trace elements. Though, in natural ecosystems, AMF undergo tripartite associations with host plants and micoorganisms (Bacteria and Fungi) living in rhizosphere (the narrow region of soil surounding the plant roots), endosphere (inside roots) and mycosphere (on the surface AMF mycelia), which some of them play a key role on translocation, immobilization and/or degradation of organic and inorganic pollutants. Consequently, the diversity and community structures of AMF and their associated microorganisms are influenced by the composition and concentration of pollutants and exudates released by the three partners (AMF, bacteria and plant roots). However, little is known about the diversity of AMF and their associated microorganisms in polluted soils and the interaction between AMF and these microorganisms remains poorly understood both in natural and contaminated areas. In this context, the objectives of my thesis were to: i) study the diversity of AMF and their associated microorganisms in PHP contaminated soils, ii) study the variation in diversity and community structures of AMF and their associated microorganisms across plant species identity and PHP concentrations, iii) study the correlations (covariations) between AMF species and their associated microorganisms and iv) compare microbial community structures of PHP contaminated soils and roots with those associated with AMF spores in order to determine if the microbial communities shaped on the surface of AMF spores and mycelia are different from those identified in soil and roots. To do so, AMF spores and/or their intraradical propagules were harvested from rhizospheric soil and roots of three plant species growing spontaneously in three distinct waste decantation basins of a former petrochemical plant located on the south shore of the St-Lawrence River, near Montreal. The harvested spores and propagules, as well as samples of soils and roots were subjected to PCR (we target 16S rRNA genes for bacteria, 18S rRNA genes for AMF and ITS regions for the other fungi), cloning, Sanger sequencing or 454 high throughput sequencing. Then, bioinformatics and statistics were performed to evaluate the effects of biotic and abiotic driving forces on AMF and their associated microbial communities. My results showed high fungal and bacterial diversity associated with AMF spores and propagules in PHP contaminated soils. I also observed that the microbial community structures associated with AMF spores were significantly affected by plant species identity and PHP concentrations. Furthermore, I observed positive and negative correlations between some AMF species and some AMF-associated microorganisms, suggesting that in addition to PHP concentrations and plant species identity, AMF species may also play a key role in shaping the microbial community surrounding their spores. Comparisons between the AMF spore-associated microbiome and the whole microbiome found in rhizospheric soil and roots showed that AMF spores recruit a microbiome differing from those found in the surrounding soil and roots. Overall, my PhD project brings a new level of knowledge on AMF diversity on extremely polluted environment and demonstrates that interaction of AMF and their associated microbes is much complex that we though previously. Further investigations are needed to better understand how AMF select and reward their associated microbes in different environments.