A intensificação das atividades humanas nas últimas décadas tem gerado um acelerado aumento na produção de resíduos sólidos urbanos (lixo), tornando-se um grave problema para as administrações públicas e para a sociedade. O aumento desordenado da população e o crescimento sem planejamento de grandes núcleos urbanos dificultam as ações de manejo dos resíduos; além disso, o uso de lixões nos grandes centros urbanos ainda é uma prática comum, o que gera problemas de saúde e ambientais. A decomposição da matéria orgânica promove a liberação do biogás, cujos principais constituintes são o gás carbônico e o metano, que corresponde a cerca de 50% e é um gás de efeito estufa, cuja emissão acarreta no aquecimento global. Além disso, gera odores desagradáveis e oferece riscos de explosão. Os aterros sanitários são considerados atualmente uma alternativa das mais interessantes para geração do biogás, visto que podem dispor de técnicas de captação dos gases liberados através de dutos de captação e queima posterior em flares, onde o metano, principal constituinte do biogás é transformado em gás carbônico, que possui um potencial de aquecimento global cerca de 20 vezes menor que o metano. Nestes aterros também existem dutos para captação do chorume, líquido proveniente da decomposição de resíduos orgânicos que se não for devidamente coletado, acarreta poluição dos recursos hídricos. Além da oportunidade de reduzir os danos ambientais é possível utilizar o biogás como combustível, gerando energia elétrica. Portanto, neste estudo é avaliado o potencial de geração de biogás do Aterro Essencis CTR Caieiras, na cidade de Caieiras, SP, e a viabilidade técnica e econômica da implantação de um projeto de geração de energia elétrica com o biogás proveniente do mesmo, por meio de um estudo de caso. Este estudo mostrou que a metodologia utilizada para quantificar o potencial de biogás do aterro em questão aproxima-se do real captado e também que a CTR Caieiras possui um alto potencial de geração de energia elétrica. Além disto, o grupo motogerador de 230 kW instalado no aterro é viável do ponto de vista econômico, podendo apresentar melhores resultados com a instalação de grupos motogeradores de maior porte. / The intensification of human activities in the last few decades has brought about an accelerated increase in the production of urban solid wastes (garbage), becoming a serious problem for the public administrations and society. The disorderly increase in population and the unplanned growth of huge urban nuclei makes it difficult for the waste management actions; in addition, the use of dump areas in the major urban centers is still a common practice, what causes health and environmental problems. The decomposition of the organic matter releases biogas, which main constituents are the carbonic gas and methane, corresponding to approximately 50% and is a greenhouse gas, which emission causes global heating. In addition, it generates unpleasant odors and presents explosion risks. The sanitary landfills are currently regarded as one of the most interesting alternatives for biogas generation, as they can rely on techniques to capture the gases released, through a capturing ducts and subsequent burning in flares, where the methane - biogas main constituent - is transformed into carbonic gas which global heating potential is approximately 20 times lower than methane. Ducts are in place at these landfills to capture the leachate, a liquid deriving from the decomposition of organic wastes which, if not duly collected, pollutes the hydrological resources. Besides the opportunity to reduce the environmental damages, it is possible to use biogas as a fuel to generate electric power. Therefore, this study assesses the potential biogas generation of the Essencis Landfill CTR Caieiras, in the city of Caieiras (SP), as well as the technical and economic feasibility for the deployment of an electric power generation project with the biogas deriving from same, by means of a case study. This study has showed that the methodology used in order to quantify the potential biogas from the landfill at issue is close to the actually captured one, and also that the CTR Caieiras has a high potential for electric power generation. In addition, the 230 kW power generator installed at the landfill is feasible, from the economic point of view, and may present better results with the installation of greater size power generators.

A intensificação das atividades humanas nas últimas décadas tem gerado um acelerado aumento na produção de resíduos sólidos urbanos (lixo), tornando-se um grave problema para as administrações públicas e para a sociedade. O aumento desordenado da população e o crescimento sem planejamento de grandes núcleos urbanos dificultam as ações de manejo dos resíduos; além disso, o uso de lixões nos grandes centros urbanos ainda é uma prática comum, o que gera problemas de saúde e ambientais. A decomposição da matéria orgânica promove a liberação do biogás, cujos principais constituintes são o gás carbônico e o metano, que corresponde a cerca de 50% e é um gás de efeito estufa, cuja emissão acarreta no aquecimento global. Além disso, gera odores desagradáveis e oferece riscos de explosão. Os aterros sanitários são considerados atualmente uma alternativa das mais interessantes para geração do biogás, visto que podem dispor de técnicas de captação dos gases liberados através de dutos de captação e queima posterior em flares, onde o metano, principal constituinte do biogás é transformado em gás carbônico, que possui um potencial de aquecimento global cerca de 20 vezes menor que o metano. Nestes aterros também existem dutos para captação do chorume, líquido proveniente da decomposição de resíduos orgânicos que se não for devidamente coletado, acarreta poluição dos recursos hídricos. Além da oportunidade de reduzir os danos ambientais é possível utilizar o biogás como combustível, gerando energia elétrica. Portanto, neste estudo é avaliado o potencial de geração de biogás do Aterro Essencis CTR Caieiras, na cidade de Caieiras, SP, e a viabilidade técnica e econômica da implantação de um projeto de geração de energia elétrica com o biogás proveniente do mesmo, por meio de um estudo de caso. Este estudo mostrou que a metodologia utilizada para quantificar o potencial de biogás do aterro em questão aproxima-se do real captado e também que a CTR Caieiras possui um alto potencial de geração de energia elétrica. Além disto, o grupo motogerador de 230 kW instalado no aterro é viável do ponto de vista econômico, podendo apresentar melhores resultados com a instalação de grupos motogeradores de maior porte. / The intensification of human activities in the last few decades has brought about an accelerated increase in the production of urban solid wastes (garbage), becoming a serious problem for the public administrations and society. The disorderly increase in population and the unplanned growth of huge urban nuclei makes it difficult for the waste management actions; in addition, the use of dump areas in the major urban centers is still a common practice, what causes health and environmental problems. The decomposition of the organic matter releases biogas, which main constituents are the carbonic gas and methane, corresponding to approximately 50% and is a greenhouse gas, which emission causes global heating. In addition, it generates unpleasant odors and presents explosion risks. The sanitary landfills are currently regarded as one of the most interesting alternatives for biogas generation, as they can rely on techniques to capture the gases released, through a capturing ducts and subsequent burning in flares, where the methane - biogas main constituent - is transformed into carbonic gas which global heating potential is approximately 20 times lower than methane. Ducts are in place at these landfills to capture the leachate, a liquid deriving from the decomposition of organic wastes which, if not duly collected, pollutes the hydrological resources. Besides the opportunity to reduce the environmental damages, it is possible to use biogas as a fuel to generate electric power. Therefore, this study assesses the potential biogas generation of the Essencis Landfill CTR Caieiras, in the city of Caieiras (SP), as well as the technical and economic feasibility for the deployment of an electric power generation project with the biogas deriving from same, by means of a case study. This study has showed that the methodology used in order to quantify the potential biogas from the landfill at issue is close to the actually captured one, and also that the CTR Caieiras has a high potential for electric power generation. In addition, the 230 kW power generator installed at the landfill is feasible, from the economic point of view, and may present better results with the installation of greater size power generators.

O presente trabalho, apresenta o estudo da produção e aproveitamento energético do biogás produzido no Aterro Sanitário de Palmas, Tocantins, em conjunto com o monitoramento ambiental da qualidade dos recursos hídricos superficiais e subterrâneos da área de interferência direta do Aterro Sanitário, e a verificação da conformidade ambiental do empreendimento por meio do Índice de Qualidade de Aterros de Resíduos – IQR. As amostras de águas subterrâneas e superficiais foram coletadas no mês de abril de 2018 nos poços de monitoramento instalados no Aterro Sanitário, seguindo as normas e legislações ambientais vigentes inerentes a temática abordada. Assim, são apresentados os resultados obtidos para os parâmetros pH, temperatura, sólidos totais, sólidos suspensos e sólidos voláteis, turbidez, alcalinidade, gás arsênio dissolvido no meio líquido, os cianetos, e os metais: bário, cádmio, chumbo, cobre, cromo, ferro, mercúrio e níquel, realizados em ambas as amostras de águas superficiais e subterrâneas realizadas pelo desenvolvimento do presente estudo. O estudo de geração de biogás produzido pelo Aterro Sanitário foi conduzido conforme os dados disponibilizados pelo município acerca da quantidade e qualidade dos resíduos dispostos no Aterro Sanitário, além das condições climáticas locais, que interferem diretamente na estabilização da matéria orgânica confinada no interior do maciço de resíduos, o que de forma direta, interfere na geração do biogás pelo Aterro Sanitário. A verificação do Índice de Qualidade de Aterros de Resíduos – IQR, deu-se por meio da verificação das condicionantes presentes no indicador, além de informações colhidas in-loco e repassadas pelo Economista Antônio Adeluzio Gomes Azevedo, técnico operacional do Aterro Sanitário. Conclui-se assim, com o desenvolvimento do presente estudo, que as águas do lençol freático e superficiais na área de interferência direta do Aterro Sanitário de Palmas - TO, não possuem poluição/contaminação decorrentes do uso atual da área como Aterro Sanitário, com base nos dados reportados na literatura e confirmados por meio da execução do presente estudo. A aferição do IQR no Aterro Sanitário de Palmas – TO, apresentou um somatório de 9,3 pontos, refletindo assim, em condições adequadas de acomodação final dos resíduos sólidos urbanos do município. No tocante a geração de biogás, torna-se possível abastecer cerca de 3.251 residências com energia elétrica gerada pelo biogás, transmitindo assim, na real viabilidade do aproveitamento energético do biogás gerado pelo Aterro Sanitário de Palmas, Tocantins. / The present work presents the study of the energy production and use of the biogas produced at Palmas Landfill, Tocantins, together with the environmental monitoring of the quality of the surface and groundwater resources of the area of direct interference of the Landfill, and the verification of the environmental compliance of the project through the Residual Landfill Quality Index - RQI. The groundwater and surface water samples were collected in April 2018 in the monitoring wells installed in the Sanitary Landfill, following the current norms and environmental legislation inherent to the subject matter. Thus, the results obtained for the parameters pH, temperature, total solids, suspended solids and volatile solids, turbidity, alkalinity, arsenic gas dissolved in the liquid medium, cyanides, and metals are presented: barium, cadmium, lead, copper, chromium, iron, mercury and nickel, performed in both the surface and groundwater samples carried out by the development of the present study. The study of biogas production produced by the Landfill was conducted according to the data provided by the municipality about the quantity and quality of the residues disposed in the Sanitary Landfill, in addition to the local climatic conditions, that directly interfere in the stabilization of the organic matter confined inside the massif of waste, which in a direct way, interferes with the generation of biogas by Landfill. The verification of the Residual Landfill Quality Index (RQI), was verified through the verification of the conditioners present in the indicator, as well as information collected locally and passed on by the Economist Antônio Adeluzio Gomes Azevedo, an operational technician of the Landfill. It is concluded, with the development of the present study, that the ground water and surface waters in the area of direct interference of the Sanitary Landfill of Palmas - TO, do not have pollution/contamination resulting from the current use of the area as Landfill, based on in the data reported in the literature and confirmed through the execution of the present study. The RQI measurement at Palmas Sanitary Landfill - TO, presented a sum of 9.3 points, reflecting, in this way, adequate conditions for final accommodation of municipal solid waste. With regard to the generation of biogas, it is possible to supply about 3,251 residences with electricity generated by biogas, thus transmitting, in the real viability of the energy utilization of the biogas generated by the Landfill of Palmas, Tocantins.

Il est reconnu que le benzène, le toluène, l’éthylbenzène et les isomères du xylène, composés organiques volatils (COVs) communément désignés BTEX, produisent des effets nocifs sur la santé humaine et sur les végétaux dépendamment de la durée et des niveaux d’exposition. Le benzène en particulier est classé cancérogène et une exposition à des concentrations supérieures à 64 g/m3 de benzène peut être fatale en 5–10 minutes. Par conséquent, la mesure en temps réel des BTEX dans l’air ambiant est essentielle pour détecter rapidement un danger associé à leur émission dans l’air et pour estimer les risques potentiels pour les êtres vivants et pour l’environnement. Dans cette thèse, une méthode d’analyse en temps réel des BTEX dans l’air ambiant a été développée et validée. La méthode est basée sur la technique d’échantillonnage direct de l’air couplée avec la spectrométrie de masse en tandem utilisant une source d’ionisation chimique à pression atmosphérique (APCI-MS/MS directe). La validation analytique a démontré la sensibilité (limite de détection LDM 1–2 μg/m3), la précision (coefficient de variation CV < 10%), l’exactitude (exactitude > 95%) et la sélectivité de la méthode. Des échantillons d’air ambiant provenant d’un site d’enfouissement de déchets industriels et de divers garages d’entretien automobile ont été analysés par la méthode développée. La comparaison des résultats avec ceux obtenus par la technique de chromatographie gazeuse on-line couplée avec un détecteur à ionisation de flamme (GC-FID) a donné des résultats similaires. La capacité de la méthode pour l’évaluation rapide des risques potentiels associés à une exposition aux BTEX a été prouvée à travers une étude de terrain avec analyse de risque pour la santé des travailleurs dans trois garages d’entretien automobile et par des expériences sous atmosphères simulées. Les concentrations mesurées dans l’air ambiant des garages étaient de 8,9–25 µg/m3 pour le benzène, 119–1156 µg/m3 pour le toluène, 9–70 µg/m3 pour l’éthylbenzène et 45–347 µg/m3 pour les xylènes. Une dose quotidienne environnementale totale entre 1,46 10-3 et 2,52 10-3 mg/kg/jour a été déterminée pour le benzène. Le risque de cancer lié à l’exposition environnementale totale au benzène estimé pour les travailleurs étudiés se situait entre 1,1 10-5 et 1,8 10-5. Une nouvelle méthode APCI-MS/MS a été également développée et validée pour l’analyse directe de l’octaméthylcyclotétrasiloxane (D4) et le décaméthylcyclopentasiloxane (D5) dans l’air et les biogaz. Le D4 et le D5 sont des siloxanes cycliques volatils largement utilisés comme solvants dans les processus industriels et les produits de consommation à la place des COVs précurseurs d’ozone troposphérique tels que les BTEX. Leur présence ubiquitaire dans les échantillons d’air ambiant, due à l’utilisation massive, suscite un besoin d’études de toxicité. De telles études requièrent des analyses qualitatives et quantitatives de traces de ces composés. Par ailleurs, la présence de traces de ces substances dans un biogaz entrave son utilisation comme source d’énergie renouvelable en causant des dommages coûteux à l’équipement. L’analyse des siloxanes dans un biogaz s’avère donc essentielle pour déterminer si le biogaz nécessite une purification avant son utilisation pour la production d’énergie. La méthode développée dans cette étude possède une bonne sensibilité (LDM 4–6 μg/m3), une bonne précision (CV < 10%), une bonne exactitude (> 93%) et une grande sélectivité. Il a été également démontré qu’en utilisant cette méthode avec l’hexaméthyl-d18-disiloxane comme étalon interne, la détection et la quantification du D4 et du D5 dans des échantillons réels de biogaz peuvent être accomplies avec une meilleure sensibilité (LDM ~ 2 μg/m3), une grande précision (CV < 5%) et une grande exactitude (> 97%). Une variété d’échantillons de biogaz prélevés au site d’enfouissement sanitaire du Complexe Environnemental de Saint-Michel à Montréal a été analysée avec succès par cette nouvelle méthode. Les concentrations mesurées étaient de 131–1275 µg/m3 pour le D4 et 250–6226 µg/m3 pour le D5. Ces résultats représentent les premières données rapportées dans la littérature sur la concentration des siloxanes D4 et D5 dans les biogaz d’enfouissement en fonction de l’âge des déchets. / It is known that benzene, toluene, ethylbenzene and xylene isomers, volatile organic compounds (VOCs) commonly called BTEX, have toxic health effects on humans and plants depending on duration and levels of exposure. Benzene in particular is classified carcinogenic, and exposure to benzene at concentrations above 64 g/m3 can be fatal within 5–10 minutes. Therefore, real-time monitoring of BTEX in ambient air is essential for the early warning detection associated with their release and in estimating the potential exposure risks to living beings and the environment. In this thesis, a real-time analysis method for BTEX in ambient air was developed and validated. The method is based on the direct-air sampling technique coupled with tandem mass spectrometry using atmospheric pressure chemical ionization (direct APCI-MS/MS). Validation of the method has shown that it is sensitive (limit of detection LOD 1–2 μg/m3), precise (relative standard deviation RSD < 10%), accurate (accuracy > 95%) and selective. Ambient air samples from an industrial waste landfill site and various automobile repair shops were analyzed by the developed method. Comparison of results with those obtained by online gas chromatography coupled with a flame ionization detector (GC-FID) technique exhibited similar results. The capacity of the method for the fast evaluation of potential risks associated with an exposure to BTEX has been demonstrated through a field study with health risk assessment for workers at three automobile repair shops and through experiments under simulated atmospheres. Concentrations measured in the ambient air of the garages were in the ranges of 8.9–25 µg/m3 for benzene, 119–1156 µg/m3 for toluene, 9–70 µg/m3 for ethylbenzene, and 45–347 µg/m3 for xylenes. A total environmental daily dose of 1.46 10-3–2.52 10-3 mg/kg/day was determined for benzene. The estimated cancer risk due to the total environmental exposure to benzene was between 1.1 10-5 and 1.8 10-5 for the workers studied. A novel APCI-MS/MS method was also developed and validated for the direct analysis of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in air and biogases. D4 and D5 are cyclic volatile siloxanes widely used in industrial processes and consumer products as replacement solvents for the tropospheric ozone forming VOCs, such as BTEX. Their ubiquitous presence in ambient air samples, due to the growing consumption, raises the need for toxicity studies which require qualitative and quantitative trace analysis of these compounds. Furthermore, the presence of trace amounts of these substances in a biogas hampers its use as a source of renewable energy by causing expensive damages to the equipment. Thus, siloxane analysis of the biogas is essential in determining if purification is needed before the use for energy production. The method developed in this study for these aims has good sensitivity (LOD 4–6 μg/m3), good precision (RSD < 10%), good accuracy (> 93%) and high selectivity. It was also shown that by using this method with hexamethyl-d18-disiloxane as an internal standard, detection and quantification of D4 and D5 in real biogas samples can be done with a better sensitivity (LOD ~ 2 μg/m3), high precision (RSD < 5%), and high accuracy (> 97%). Various biogas samples collected from the landfill site of the Complexe Environnemental de Saint-Michel in Montreal have been successfully analyzed by this new method. Concentrations measured were in the ranges of 131–1275 µg/m3 for D4 and 250–6226 µg/m3 for D5. These results represent the first primary-literature-reported data on siloxanes D4 and D5 contents of landfill-derived biogases as a function of the refuse age.

Il est reconnu que le benzène, le toluène, l’éthylbenzène et les isomères du xylène, composés organiques volatils (COVs) communément désignés BTEX, produisent des effets nocifs sur la santé humaine et sur les végétaux dépendamment de la durée et des niveaux d’exposition. Le benzène en particulier est classé cancérogène et une exposition à des concentrations supérieures à 64 g/m3 de benzène peut être fatale en 5–10 minutes. Par conséquent, la mesure en temps réel des BTEX dans l’air ambiant est essentielle pour détecter rapidement un danger associé à leur émission dans l’air et pour estimer les risques potentiels pour les êtres vivants et pour l’environnement. Dans cette thèse, une méthode d’analyse en temps réel des BTEX dans l’air ambiant a été développée et validée. La méthode est basée sur la technique d’échantillonnage direct de l’air couplée avec la spectrométrie de masse en tandem utilisant une source d’ionisation chimique à pression atmosphérique (APCI-MS/MS directe). La validation analytique a démontré la sensibilité (limite de détection LDM 1–2 μg/m3), la précision (coefficient de variation CV < 10%), l’exactitude (exactitude > 95%) et la sélectivité de la méthode. Des échantillons d’air ambiant provenant d’un site d’enfouissement de déchets industriels et de divers garages d’entretien automobile ont été analysés par la méthode développée. La comparaison des résultats avec ceux obtenus par la technique de chromatographie gazeuse on-line couplée avec un détecteur à ionisation de flamme (GC-FID) a donné des résultats similaires. La capacité de la méthode pour l’évaluation rapide des risques potentiels associés à une exposition aux BTEX a été prouvée à travers une étude de terrain avec analyse de risque pour la santé des travailleurs dans trois garages d’entretien automobile et par des expériences sous atmosphères simulées. Les concentrations mesurées dans l’air ambiant des garages étaient de 8,9–25 µg/m3 pour le benzène, 119–1156 µg/m3 pour le toluène, 9–70 µg/m3 pour l’éthylbenzène et 45–347 µg/m3 pour les xylènes. Une dose quotidienne environnementale totale entre 1,46 10-3 et 2,52 10-3 mg/kg/jour a été déterminée pour le benzène. Le risque de cancer lié à l’exposition environnementale totale au benzène estimé pour les travailleurs étudiés se situait entre 1,1 10-5 et 1,8 10-5. Une nouvelle méthode APCI-MS/MS a été également développée et validée pour l’analyse directe de l’octaméthylcyclotétrasiloxane (D4) et le décaméthylcyclopentasiloxane (D5) dans l’air et les biogaz. Le D4 et le D5 sont des siloxanes cycliques volatils largement utilisés comme solvants dans les processus industriels et les produits de consommation à la place des COVs précurseurs d’ozone troposphérique tels que les BTEX. Leur présence ubiquitaire dans les échantillons d’air ambiant, due à l’utilisation massive, suscite un besoin d’études de toxicité. De telles études requièrent des analyses qualitatives et quantitatives de traces de ces composés. Par ailleurs, la présence de traces de ces substances dans un biogaz entrave son utilisation comme source d’énergie renouvelable en causant des dommages coûteux à l’équipement. L’analyse des siloxanes dans un biogaz s’avère donc essentielle pour déterminer si le biogaz nécessite une purification avant son utilisation pour la production d’énergie. La méthode développée dans cette étude possède une bonne sensibilité (LDM 4–6 μg/m3), une bonne précision (CV < 10%), une bonne exactitude (> 93%) et une grande sélectivité. Il a été également démontré qu’en utilisant cette méthode avec l’hexaméthyl-d18-disiloxane comme étalon interne, la détection et la quantification du D4 et du D5 dans des échantillons réels de biogaz peuvent être accomplies avec une meilleure sensibilité (LDM ~ 2 μg/m3), une grande précision (CV < 5%) et une grande exactitude (> 97%). Une variété d’échantillons de biogaz prélevés au site d’enfouissement sanitaire du Complexe Environnemental de Saint-Michel à Montréal a été analysée avec succès par cette nouvelle méthode. Les concentrations mesurées étaient de 131–1275 µg/m3 pour le D4 et 250–6226 µg/m3 pour le D5. Ces résultats représentent les premières données rapportées dans la littérature sur la concentration des siloxanes D4 et D5 dans les biogaz d’enfouissement en fonction de l’âge des déchets. / It is known that benzene, toluene, ethylbenzene and xylene isomers, volatile organic compounds (VOCs) commonly called BTEX, have toxic health effects on humans and plants depending on duration and levels of exposure. Benzene in particular is classified carcinogenic, and exposure to benzene at concentrations above 64 g/m3 can be fatal within 5–10 minutes. Therefore, real-time monitoring of BTEX in ambient air is essential for the early warning detection associated with their release and in estimating the potential exposure risks to living beings and the environment. In this thesis, a real-time analysis method for BTEX in ambient air was developed and validated. The method is based on the direct-air sampling technique coupled with tandem mass spectrometry using atmospheric pressure chemical ionization (direct APCI-MS/MS). Validation of the method has shown that it is sensitive (limit of detection LOD 1–2 μg/m3), precise (relative standard deviation RSD < 10%), accurate (accuracy > 95%) and selective. Ambient air samples from an industrial waste landfill site and various automobile repair shops were analyzed by the developed method. Comparison of results with those obtained by online gas chromatography coupled with a flame ionization detector (GC-FID) technique exhibited similar results. The capacity of the method for the fast evaluation of potential risks associated with an exposure to BTEX has been demonstrated through a field study with health risk assessment for workers at three automobile repair shops and through experiments under simulated atmospheres. Concentrations measured in the ambient air of the garages were in the ranges of 8.9–25 µg/m3 for benzene, 119–1156 µg/m3 for toluene, 9–70 µg/m3 for ethylbenzene, and 45–347 µg/m3 for xylenes. A total environmental daily dose of 1.46 10-3–2.52 10-3 mg/kg/day was determined for benzene. The estimated cancer risk due to the total environmental exposure to benzene was between 1.1 10-5 and 1.8 10-5 for the workers studied. A novel APCI-MS/MS method was also developed and validated for the direct analysis of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) in air and biogases. D4 and D5 are cyclic volatile siloxanes widely used in industrial processes and consumer products as replacement solvents for the tropospheric ozone forming VOCs, such as BTEX. Their ubiquitous presence in ambient air samples, due to the growing consumption, raises the need for toxicity studies which require qualitative and quantitative trace analysis of these compounds. Furthermore, the presence of trace amounts of these substances in a biogas hampers its use as a source of renewable energy by causing expensive damages to the equipment. Thus, siloxane analysis of the biogas is essential in determining if purification is needed before the use for energy production. The method developed in this study for these aims has good sensitivity (LOD 4–6 μg/m3), good precision (RSD < 10%), good accuracy (> 93%) and high selectivity. It was also shown that by using this method with hexamethyl-d18-disiloxane as an internal standard, detection and quantification of D4 and D5 in real biogas samples can be done with a better sensitivity (LOD ~ 2 μg/m3), high precision (RSD < 5%), and high accuracy (> 97%). Various biogas samples collected from the landfill site of the Complexe Environnemental de Saint-Michel in Montreal have been successfully analyzed by this new method. Concentrations measured were in the ranges of 131–1275 µg/m3 for D4 and 250–6226 µg/m3 for D5. These results represent the first primary-literature-reported data on siloxanes D4 and D5 contents of landfill-derived biogases as a function of the refuse age.