Compostos butílicos de estanho (BTs) estão na lista dos contaminantes impactantes relacionados ao ambiente marinho. Sua ampla distribuição associada à elevada toxicidade faz com que o monitoramento desses compostos no ambiente costeiro seja de fundamental importância. A ocorrência de BTs foi verificada em sedimentos superficiais, material particulado em suspensão e nos tecidos (fígado e brânquias) de três espécies de bagres estuarinos: Cathorops spixii, Aspistor luniscutis e Genidens genidens; amostrados em 8 estuários da região sul e sudeste brasileira. As análises foram realizadas através de GC-PFPD, seguindo padrões de controle de qualidade analítico e onde foi constatada a ocorrência de efeito matriz sobre o sistema analítico a partir da quantificação das amostras de tecido. Dentre os estuários amostrados, verificou-se um maior impacto dos BTs sobre os sistemas estuarinos de Paranaguá e Itajaí, em decorrência da presença destes compostos em todos os compartimentos ambientais analisados. As três espécies investigadas puderam ser consideradas como biomonitoras da presença de BTs no ambiente, uma vez que são passíveis de assimilação destes compostos, mesmo em organismos amostrados em regiões distantes de potencias fontes de entrada. Os efeitos sobre a fisiologia de C. spixii amostrado em Paranaguá também foi investigada a partir do uso de biomarcadores no fígado desses organismos, constatando um impacto associado à presença destes contaminantes no sistema. / Butyltin compounds (BTs) are in the list of related contaminants striking marine environment. Their widespread distribution associated with high toxicity causes the monitoring of fundamental importance. The occurrence of BTs were checked through superficial sediments, suspended particulate matter and tissues (liver and gill) analysis on three estuarine catfishes: Cathorops spixii, Aspistor luniscutis e Genidens genidens; sampled in eight estuaries from Brazilian south and southeast coast. Analysis were carried by GC-PFPD, following quality control procedures, where was verified the presence of matrix effect over the system from tissues quantification. Among estuaries, the major impact was found in Paranaguá-PR and Itajaí-SC, due the presence of these compounds in all investigated compartments. These three catfish species have shown good biomonitors of BTs presence once were liable of uptake, even in groups sampled far from potential BTs sources. The effects over C. spixii physiology were also checked in Paranaguá from the use of biomarkers on liver of these organisms, noting the impact related with the presence of these compounds on the system.

Compostos butílicos de estanho (BTs) estão na lista dos contaminantes impactantes relacionados ao ambiente marinho. Sua ampla distribuição associada à elevada toxicidade faz com que o monitoramento desses compostos no ambiente costeiro seja de fundamental importância. A ocorrência de BTs foi verificada em sedimentos superficiais, material particulado em suspensão e nos tecidos (fígado e brânquias) de três espécies de bagres estuarinos: Cathorops spixii, Aspistor luniscutis e Genidens genidens; amostrados em 8 estuários da região sul e sudeste brasileira. As análises foram realizadas através de GC-PFPD, seguindo padrões de controle de qualidade analítico e onde foi constatada a ocorrência de efeito matriz sobre o sistema analítico a partir da quantificação das amostras de tecido. Dentre os estuários amostrados, verificou-se um maior impacto dos BTs sobre os sistemas estuarinos de Paranaguá e Itajaí, em decorrência da presença destes compostos em todos os compartimentos ambientais analisados. As três espécies investigadas puderam ser consideradas como biomonitoras da presença de BTs no ambiente, uma vez que são passíveis de assimilação destes compostos, mesmo em organismos amostrados em regiões distantes de potencias fontes de entrada. Os efeitos sobre a fisiologia de C. spixii amostrado em Paranaguá também foi investigada a partir do uso de biomarcadores no fígado desses organismos, constatando um impacto associado à presença destes contaminantes no sistema. / Butyltin compounds (BTs) are in the list of related contaminants striking marine environment. Their widespread distribution associated with high toxicity causes the monitoring of fundamental importance. The occurrence of BTs were checked through superficial sediments, suspended particulate matter and tissues (liver and gill) analysis on three estuarine catfishes: Cathorops spixii, Aspistor luniscutis e Genidens genidens; sampled in eight estuaries from Brazilian south and southeast coast. Analysis were carried by GC-PFPD, following quality control procedures, where was verified the presence of matrix effect over the system from tissues quantification. Among estuaries, the major impact was found in Paranaguá-PR and Itajaí-SC, due the presence of these compounds in all investigated compartments. These three catfish species have shown good biomonitors of BTs presence once were liable of uptake, even in groups sampled far from potential BTs sources. The effects over C. spixii physiology were also checked in Paranaguá from the use of biomarkers on liver of these organisms, noting the impact related with the presence of these compounds on the system.

Cheddar Cheese samples (good cheese, weak cheese, cheese made with pasteurized milk, cheese made with heat-shocked milk, cheese from production plant A, cheese from production plant B, cheese made with adjunct culture, and cheese made without adjunct culture), were evaluated during the ripening stage. Proteolysis was studied by a fractionation scheme, resulting in an insoluble fraction analyzed by urea polyacrylamide gel electrophoresis (Urea-PAGE), and a soluble fraction which was further investigated through water soluble nitrogen (WSN), trichloroacetic acid soluble nitrogen (TCA-SN) and phosphotungstic acid soluble nitrogen (PTA-SN) analyzed by total Kjeldahl nitrogen content (TKN). Reversed phase high performance liquid chromatography (RP-HPLC) was used to study the peptide profile of the water soluble fraction. Lipolyisis was studied by levels of individual free fatty acids determined through gas chromatography-flame ionization detection (GC-FID) after isolation employing solid phase extraction (SPE). Volatile sulfur compounds were studied using head space solid phase micro-extraction (SPME) coupled with gas chromatography-pulsed flame photometric detection (PFPD). It was found that Urea-PAGE is capable to differentiate samples according their age, but cannot discriminate samples regarding the treatment assessed, quality or origin of the samples. However, measurements of total Kjeldahl Nitrogen (TKN) of the WSN, TCA-SN, and PTA-SN fractions, and the principal component analysis of the RP-HPLC peptide profile of the WSN fraction, revealed differences in the rate and pattern of proteolysis for each one of the manufacturing cases. Good cheese, cheese produce in plant TCCA, cheese made in plant CRP with adjunct culture isolated from plant TCCA cheese, and cheese made with heat-shocked milk developed higher level of total nitrogen for the WSN, TCA-SN and PTA-SN fractions, indicating that primary and secondary proteolysis were faster for these samples. This is supported by a PCA model with three principal components that account for the 80-83% of the variability of the data from the RP-HPLC peptide profile analysis, which discriminates the samples according to age and manufacturing practice. In addition, FFA profiles demonstrated higher levels of low and medium chain free fatty acids for good cheese, cheese produce in plant TCCA, cheese made in plant CRP with adjunct culture, and cheese made with heat-shocked milk samples, which suggest faster lipolysis during ripening. The Volatile Sulfur Compounds (VSC) analysis showed higher levels of DMS and MeSH and lower levels of H2S, suggesting faster catabolism of sulfur containing amino acids in good cheese, cheese produce in plant TCCA, cheese made in plant CRP with adjunct culture, and cheese made with heat-shocked milk. / Graduation date: 2013