Avaliação da qualidade dos sedimentos por meio e biomarcadores geoquímicos e elementos-traço em amostras do estuário do Rio Itajaí-Açu e determinação de contaminantes em matrizes de resíduos sólidos

Tese (doutorado) - Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas, Programa de Pós-Graduação em Química, Florianópolis, 2014.O sistema estuarino do rio Itajaí-Açu, localizado na região Sul do Brasil, é afetado por atividades industriais e de dragagem, que podem causar remobilização dos poluentes acumulados ao longo do tempo no sedimento. Por isso, biomarcadores geoquímicos e elementos-traço foram avaliados qualitativamente e quantitativamente em doze amostras superficiais de sedimento. Os níveis de n-alcanos, hidrocarbonetos policíclicos aromáticos (HPA) e esteróis foram obtidos a fim de identificar suas fontes e a possível contaminação do ambiente por combustíveis fósseis e esgoto doméstico. As concentrações totais variaram entre 0,49 e 69,71 ?g g-1 para os n-alcanos e de 63,89 a 1458,99 ng g-1 para os HPA. As concentrações obtidas para este estuário são semelhantes a de outros ambientes estuarinos e costeiros ao redor do mundo. Comparando os níveis de HPA com os indicadores do Guia de Qualidade de Sedimentos, os resultados apontaram que a ocorrência de efeitos adversos à biota pode ocorrer raramente e/ou ocasionalmente. Com base nas razões diagnósticas para HPA utilizadas neste estudo, as principais fontes desses compostos são pirolíticas, embora fontes petrogênicas também tenham sido encontradas. Uma mistura complexa não resolvida foi detectada na estação 5, localizada no Porto de Itajaí, sugerindo contaminação por combustíveis fósseis. A presença de hopanos de estereoquímica ???em?todas as estações indica fontes petrogênicas nas amostras avaliadas. Esteróis foram identificados em todas as amostras, sendo os mais abundantes o colesterol, o coprostanol e o ?-sitosterol, que representam fontes tais como zooplâncton, esgoto doméstico e plantas superiores, respectivamente. A distribuição de ácidos graxos permitiu inferir a origem da matéria orgânica como predominantemente aquática, com pouca contribuição de plantas, notavelmente nas estações 7 e 8. A maior incidência de ácidos saturados com cadeias longas foi observada na estação 11, representando a contribuição de plantas nessa estação. No que diz respeito aos contaminantes inorgânicos, um procedimento de extração simples e rápido foi proposto para a determinação de elementos-traço em amostras de sedimentos por espectrometria de massa com plasma indutivamente acoplado. Ótimos resultados foram obtidos quando se submeteu 100 mg de sedimento à extração assistida por ultrassom por 15 minutos com HF a 7,50 mol L-1 e HNO3 a 3,50 mol L-1 . Limites de detecção entre 0,02 e 0,10 ?g g-1 e desvios padrão relativos inferiores a 8% foram obtidos. O método proposto foi aplicado na determinação de elementos-traço em amostras de sedimentos do estuário do rio Itajaí-Açu e as concentrações obtidas, comparadas aos referenciais do Guia de Qualidade de Sedimentos para a Proteção da Vida Aquática. Observou-se que as amostras de sedimentos avaliadas apresentam uma boa qualidade em relação a poluentes inorgânicos. Além disso, foi desenvolvida uma metodologia analítica para a determinação de benzeno, tolueno, etilbenzeno e xilenos (BTEX) em amostras de resíduos sólidos, utilizando microextração em fase sólida e cromatografia gasosa. As melhores respostas foram obtidas utilizando a fibra carboxen/polidimetilsiloxano (CAR/PDMS), tempo de extração de 20 minutos a 25 ºC e massa de resíduo de 20,0 mg. O método desenvolvido proporcionou um bom desempenho em termos de precisão (abaixo de 7% para todos os analitos), recuperação, seletividade, robustez e limites de detecção (1,8 a 21,0 ng mL-1). Além disso, é um método simples, livre de solventes e adequado para a classificação de resíduos sólidos.Abstract : The Itajaí-Açu estuarine system, located in southern Brazil, is affected by industrial and dredging activities, which can cause remobilization of the pollutants accumulated over time in the sediment. Thus, geochemical biomarkers and trace elements were studied qualitatively and quantitatively in 12 surface sediment samples. The levels of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAH) and sterols were measured in order to identify their sources and possible contamination by fossil fuels and domestic sewage. The total concentrations ranged between 0.49 and 69.71 ?g g-1 of dry weight for n-alkanes and from 63.89 to 1458.99 ng g-1 of dry weight for PAH. Concentrations in this estuary are comparable to estuarines and coastal environments around the world. Comparing the PAH levels found in the estuarine sediments with the Sediment Quality Guidelines, results indicated that adverse effects are expected to occur rarely to occasionally to the living biota. According to the calculated PAH ratios, the major sources of PAH are pyrolytic, although petrogenic was also found. Unresolved complex mixture was detected at site 5, located at the Itajaí harbor, suggesting contamination by fossil fuels. The presence of hopanes with ?? stereochemistry at all stations indicated petrogenic input. Sterols were identified in all the samples. The most abundant sterols were cholesterol, coprostanol and ?-sitosterol, suggesting sources such as zooplankton, domestic sewage and higher plants. The distribution of fatty acids allowed to infer the origin of organic matter as predominantly aquatic, with little contribution of vascular plants, notably in stations 7 and 8, which agrees with the RTA values for nalkanes. The major contribution of long chain fatty acids was observed at station 11, representing the contribution of vascular plants at these station. Regarding inorganic contaminants, a simple and fast extractionbased procedure was proposed for the determination of trace elements in sediment samples by inductively coupled plasma mass-spectrometry. Optimum results were obtained when 100 mg of sediment sample was used followed by ultrasound-assisted extraction for 15 min with 7,50 mol L-1 (HF) and 3,50 mol L-1 (HNO3). Detection limits ranging from 0,02 to 0,10 ?g g-1 and relative standard deviation lower than 8% were obtained. The proposed method was applied in the sediments of the Itajaí-Açu estuarine system and the concentrations of trace elements were compared to the Sediment Quality Guidelines. It was observed that the sediment samples evaluated show good quality regarding inorganic pollutants. In addition, an analytical methodology was developed for the determination of benzene, toluene, ethylbenzene and xylenes (BTEX) in samples of solid waste using solid phase microextraction and gas chromatography. Best results were obtained using the carboxen/polydimetrylsiloxane fiber (CAR/PDMS), extraction time of 20 min at 25 °C and 20 mg of sample. The developed method provided a good performance in terms of precision (lower than 7% for all analytes), recovery, selectivity, robustness and detection limits (1,8 to 21,0 ng mL- 1). Furthermore, it is a simple, solvent-free method suitable for the classification of solid waste

Determinação de hidrocarbonetos de petróleo em amostras de sedimentos do complexo lagunar sul Santo Antônio-Imaruí-Mirim, SC

TCC (graduação) - Universidade Federal de Santa Catarina. Centro de Ciências Físicas e Matemáticas. Curso de Química.Amostras superficiais de sedimento foram coletadas ao longo do Complexo Lagunar Sul Santo Antônio-Imaruí-Mirim. A composição química do extrato orgânico sedimentar foi analisada e caracterizada pelas técnicas de análise elementar, granulometria, cromatografia gasosa (GC/FID) e cromatografia gasosa acoplada à espectrometria de massas (GC-MS). Este estudo foi realizado com o intuito de avaliar a presença de hidrocarbonetos que indiquem a origem da matéria orgânica (biogênica e antropogênica) encontrada no sedimento. As concentrações dos hidrocarbonetos alifáticos variaram de 113 a 34.883 g g-1 em relação ao carbono orgânico total (COT). Os cromatogramas obtidos revelaram abundância de hidrocarbonetos com cadeias hidrocarbônicas longas (> C17), com predomínio de ímpares sobre os pares e máximos em C27, C29 e C31, indicando matéria orgânica de origem terrestre. Uma série de compostos do tipo triterpenóides, pertencentes ao grupo dos hopanos, foi identificada por meio do monitoramento do fragmento m/z 191. Observou-se predominância dos hopanos de estereoquímica 17(H), 21(H), mais estável termodinamicamente frente aos outros estereoisômeros, e normalmente presente em derivados de petróleo. Hidrocarbonetos policíclicos aromáticos e seus homólogos foram identificados em todas as amostras em estudo. Os valores das razões entre MetilFEN/FEN, FLUO/PIR e FLUO/(FLUO+PIR) indicaram que os HPA são de origem petrogênica e/ou pirolítica

Distribution And Sources Of Aliphatic And Polycyclic Aromatic Hydrocarbons In Surface Sediments Of Itajai-acu Estuarine System In Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)The Itajai-Acu estuarine system, located in southern Brazil, has great economic importance due to the presence of two ports (Itajai and Navegantes). This system is affected by industrial and dredging activities, which can cause the remobilization of pollutants accumulated over time in the sediment. In this context, hydrocarbons were assessed in twelve surface sediment samples. n-Alkane and polycyclic aromatic hydrocarbons (PAH) concentrations were determined by gas chromatography and their sources assessed. Total concentrations ranged between 0.50 +/- 0.04 and 69.70 +/- 3.90 mu g g(-1) dry weight (d.w.)for n-alkanes and from 63.9 +/- 12.1 to 1459.0 +/- 43.5 ng g(-1) d.w. for PAH. Most of the sediment samples presented carbon preference index (CPI) values close to unity, indicating that the area is submitted to petroleum-related sources, mainly close to Itajai harbor, where an intense unresolved complex mixture (UCM) was observed. The presence at all stations of alpha beta-hopane biomarkers also indicated petrogenic input. Based on selected PAH ratios, the sedimentary PAH composition reflects a mixture of both petrogenic and pyrolytic sources. A comparison of the PAH concentrations found in this study with those listed in the sediment quality guidelines (SQGs) indicated that adverse biological effects on the biota are rarely expected.284603614Petroleo Brasileiro S.A. (Petrobras), Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [304209/2013-9]Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2012/21395-0]Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Distribution and sources of aliphatic and polycyclic aromatic hydrocarbons in surface sediments of Itajaí-Açu estuarine system in Brazil

The Itajaí-Açu estuarine system, located in southern Brazil, has great economic importance due to the presence of two ports (Itajaí and Navegantes). This system is affected by industrial and dredging activities, which can cause the remobilization of pollutants accumulated over time in the sediment. In this context, hydrocarbons were assessed in twelve surface sediment samples. n-Alkane and polycyclic aromatic hydrocarbons (PAH) concentrations were determined by gas chromatography and their sources assessed. Total concentrations ranged between 0.50 ± 0.04 and 69.70 ± 3.90 μg g-1 dry weight (d.w.) for n-alkanes and from 63.9 ± 12.1 to 1459.0 ± 43.5 ng g-1 d.w. for PAH. Most of the sediment samples presented carbon preference index (CPI) values close to unity, indicating that the area is submitted to petroleum-related sources, mainly close to Itajaí harbor, where an intense unresolved complex mixture (UCM) was observed. The presence at all stations of αβ-hopane biomarkers also indicated petrogenic input. Based on selected PAH ratios, the sedimentary PAH composition reflects a mixture of both petrogenic and pyrolytic sources. A comparison of the PAH concentrations found in this study with those listed in the sediment quality guidelines (SQGs) indicated that adverse biological effects on the biota are rarely expected.The Itajaí-Açu estuarine system, located in southern Brazil, has great economic importance due to the presence of two ports (Itajaí and Navegantes). This system is affected by industrial and dredging activities, which can cause the remobilization of pollu28460361

Application of Solid Phase Microextraction and Gas Chromatography for the Determination of BTEX in Solid Petroleum Residues

This work describes a simple and fast method for the determination of BTEX (benzene, toluene, ethylbenzene and xylene) in solid waste and solutions obtained from leaching applying procedures detailed in the ABNT NBR 10004/2004 Brazilian standard for the classification of solid residues. The proposed method allows the direct detection of BTEX using solid-phase microextraction and gas chromatography with a flame ionization detector (HS-SPME GC/FID). Limits of quantification for BTEX showed that the developed method is suitable for the classification of solid wastes

Assessment Of Anthropogenic Contamination With Sterol Markers In Surface Sediments Of A Tropical Estuary (itajai-acu, Brazil)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)The Itajai-Acu estuarine region is one of the most important estuarine systems of south Brazil, due to the location of the Itajai Harbor, which is the major route of international trading of the state and the largest national fishing pole landing. In addition, industries as well as urban and tourism activities are potential sources of pollution in this area. In the present study, sediment samples from 12 stations along the estuarine system were collected and extracted followed by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis. Eight sterols were identified and quantified, indicating natural and anthropogenic sources. Coprostanol concentrations ranged from <4 up to 8930 ng g(-1) of dry weight sediment with higher values being observed in the area next to the Itajai Harbor and under influence of Itajai-Mirim River flow, which receives wastewater from several cities. Concentrations and selected sterol ratios were useful tools used to distinguish anthropogenic and biogenic organic matter (OM) sources in the studied area, where coprostanol concentrations higher than 500 ng g(-1) were observed in 42% of the stations analyzed, indicating strong sewage contamination. Factor analysis with principal component analysis (FA/PCA) has distinguished two different groups of samples, with high and low total sterol concentrations. FA/PCA results revealed that the stations located in the estuary were separated by PC1 because they are clearly contaminated by sewage, also pointed by coprostanol/(coprostanol + cholestanol) and coprostanol/cholesterol ratios and by the higher concentrations of fecal sterols. (C) 2015 Elsevier B.V. All rights reserved.544432438Petroleo Brasileiro S.A. (Petrobras, TC) [0050.0094316.14.9]Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [140657/2011-8]Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2012/21395-0]Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Photochemical Degradation of Diesel Oil in Water: a Comparative Study of Different Photochemical Oxidation Processes and their Degradation By-Products

This paper provides a comparative study of different photochemical oxidation processes and a detailed characterization of the by-products of diesel oil degradation performed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS). Diesel degradation was conducted in a photolytic reactor using UV, H2O2, UV/H2O2, O3 or O3/UV. The best conditions for each process were obtained applying multivariate analysis and the experimental results indicated that the O3/UV process was the most feasible for the treatment of wastewater containing diesel fuel, with a degradation percentage of > 90%. Almost complete degradation of the aromatics was achieved. Phenolic compounds were identified as by-products of the diesel samples treated with the UV, H2O2, O3 and O3/UV processes. Besides the phenolic compounds, other by-products identified included carboxylic acids and ethers in the UV/peroxide treatment, ethers in the UV irradiation treatment and ketones in the ozone treatment

Assessment Of Anthropogenic Contamination With Sterol Markers In Surface Sediments Of A Tropical Estuary (itajaí-açu, Brazil).

The Itajaí-Açu estuarine region is one of the most important estuarine systems of south Brazil, due to the location of the Itajaí Harbor, which is the major route of international trading of the state and the largest national fishing pole landing. In addition, industries as well as urban and tourism activities are potential sources of pollution in this area. In the present study, sediment samples from 12 stations along the estuarine system were collected and extracted followed by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis. Eight sterols were identified and quantified, indicating natural and anthropogenic sources. Coprostanol concentrations ranged from <4 up to 8930ngg(-1) of dry weight sediment with higher values being observed in the area next to the Itajaí Harbor and under influence of Itajaí-Mirim River flow, which receives wastewater from several cities. Concentrations and selected sterol ratios were useful tools used to distinguish anthropogenic and biogenic organic matter (OM) sources in the studied area, where coprostanol concentrations higher than 500ngg(-1) were observed in 42% of the stations analyzed, indicating strong sewage contamination. Factor analysis with principal component analysis (FA/PCA) has distinguished two different groups of samples, with high and low total sterol concentrations. FA/PCA results revealed that the stations located in the estuary were separated by PC1 because they are clearly contaminated by sewage, also pointed by coprostanol/(coprostanol+cholestanol) and coprostanol/cholesterol ratios and by the higher concentrations of fecal sterols.544432-43