Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

The polychlorinated biphenyls (PCBs) comprise a group of 209 congeners varying in the number of chlorine atoms and substitution patterns. These compounds tend to be biomagnified in foodwebs and have been shown to induce an array of effects in exposed organisms. The structural characteristics of the PCBs influence their potency as well as mechanism of action. In order to assess the biological potency of these compounds a multi-step quantitative structure-activity relationship (QSAR) procedure was used in the project described in this thesis. The ultraviolet absorption (UV) spectra were measured for all 209 PCBs, and digitised for use as physico-chemical descriptors. Interpretations of the spectra using principal component analysis (PCA) showed the number of ortho chlorine atoms and para-para substitution patterns to be significant. Additional physico-chemical descriptors were derived from semi-empirical calculations. These included various molecular energies, the ionisation potential, electron affinity, dipole moments, and the internal barrier of rotation. The internal barrier of rotation was especially useful for describing the conformation of the PCBs on a continuous scale. In total 52 physico-chemical descriptors were compiled and analysed by PCA for the tetra- to hepta-chlorinated congeners. The structural variation within these compounds was condensed into four principal properties derived from a PCA for use as design variables in a statistical design to select congeners representative for these homologue-groups. The 20 selected PCBs have been applied to study structure-specific biochemical responses in a number of bioassays, and to study the biomagnification of the PCBs in various fish species. QSARs were established using partial least squares projections to latent structures (PLS) for the PCBs potency to inhibit intercellular communication, activate respiratory burst, inhibit dopamine uptake in synaptic vesicles, compete with estradiol for binding to estrogen receptors, and induce cytochrome P4501A (CYP1A) related activities. By the systematic use of the designed set of PCBs the biological potency was screened over the chemical domain of the class of compounds. Further, sub-regions of highly potent PCBs were identified for each response measured. For risk assessment of the PCBs potency to induce dioxin-like activities the predicted induction potencies (PIPs) were calculated. In addition, two sets of PCBs were presented that specifically represent congeners of environmental relevance in combination with predicted potency to induce estrogenic and CYP1A related activities.

Water resources in South Africa are scarce, and should therefore be protected against pollutants, also from persistent organic pollutants (POPs). This is emphasised by the Stockholm Convention on POPs, which aims at reducing and ultimately eliminating POPs. South Africa signed and ratified the treaty, and it became international law on 17 May 2004. POPS are highly stable, toxic, hydrophobic and lipophilic compounds, with the ability to accumulate in biological tissues. Previous research had shown that dioxin-like POPS are present in the aquatic environments of South Africa, with the highest concentrations of these substances measured in industrialised areas of South Africa. The present study aimed at investigating the extent of polychlorinated dibenzo-para-dioxin (PCDD), polychlorinated dibenzo-furan (PCDF) and polychlorinated biphenyl (PCB) pollution in the Vaal Triangle, by targeting aquatic sediments and biota. Sediment samples were collected from the Blesbok Spruit, Taaibos Spruit, Leeu Spruit and Suikerbosrand River, and fish tissue samples were collected from Blesbok Spruit and Suikerbosrand River, to determine bio-accumulation. The samples were extracted with organic solvents, cleaned-up and fractionated. Raw extracts and fractions were analysed with the H4IIE-luc reporter gene bio-assay. This bio-assay is a rapid, sensitive and relatively cost-effective method, which measures the effects of dioxin-like compounds on rat hepatoma cells, transfected with firefly luciferase gene. Selected samples were analysed with gas chromatographylmass spectrometry (GCIMS) to confirm results. Only one site had quantifiable amounts of dioxin-like substances in the sediment, measured to be 52.35 ng/kg [Effective Concentration 50 (EC 50)]. This value exceeds many of the European and USA quality guidelines, proposed for sediments. No dioxin-like substances were found in fish tissues. The absence of PCDD/Fs and PCBs in aquatic sediments and fish tissues from the Vaal Triangle area might be due to the climatic conditions of the area, dilution effects in streams, and degradation of these compounds by UV-radiation and microbial organisms. / Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

Water resources in South Africa are scarce, and should therefore be protected against pollutants, also from persistent organic pollutants (POPs). This is emphasised by the Stockholm Convention on POPs, which aims at reducing and ultimately eliminating POPs. South Africa signed and ratified the treaty, and it became international law on 17 May 2004. POPS are highly stable, toxic, hydrophobic and lipophilic compounds, with the ability to accumulate in biological tissues. Previous research had shown that dioxin-like POPS are present in the aquatic environments of South Africa, with the highest concentrations of these substances measured in industrialised areas of South Africa. The present study aimed at investigating the extent of polychlorinated dibenzo-para-dioxin (PCDD), polychlorinated dibenzo-furan (PCDF) and polychlorinated biphenyl (PCB) pollution in the Vaal Triangle, by targeting aquatic sediments and biota. Sediment samples were collected from the Blesbok Spruit, Taaibos Spruit, Leeu Spruit and Suikerbosrand River, and fish tissue samples were collected from Blesbok Spruit and Suikerbosrand River, to determine bio-accumulation. The samples were extracted with organic solvents, cleaned-up and fractionated. Raw extracts and fractions were analysed with the H4IIE-luc reporter gene bio-assay. This bio-assay is a rapid, sensitive and relatively cost-effective method, which measures the effects of dioxin-like compounds on rat hepatoma cells, transfected with firefly luciferase gene. Selected samples were analysed with gas chromatographylmass spectrometry (GCIMS) to confirm results. Only one site had quantifiable amounts of dioxin-like substances in the sediment, measured to be 52.35 ng/kg [Effective Concentration 50 (EC 50)]. This value exceeds many of the European and USA quality guidelines, proposed for sediments. No dioxin-like substances were found in fish tissues. The absence of PCDD/Fs and PCBs in aquatic sediments and fish tissues from the Vaal Triangle area might be due to the climatic conditions of the area, dilution effects in streams, and degradation of these compounds by UV-radiation and microbial organisms. / Thesis (M. Environmental Science (Water Science))--North-West University, Potchefstroom Campus, 2007.

Introduction Neuropsychological development is a genetically guided process which is continuously modified by socio-environmental factors. This thesis aimed to study the main socio-environmental determinants of neuropsychological development in different time-periods, such in the first two years of life, during preschool, and during preadolescence. This thesis also aimed to summarize the work done in environmental epidemiology on neuropsychological development in a novel conceptual framework. Methods This thesis is based on the data of the INMA (Infancia y Medio Ambiente) Project. The main objective of this project is to evaluate the impact of environmental exposures in children’s health in 7 population-based birth cohorts in different regions of Spain. The neuropsychological development of approximate total of 2,650 children was assessed at different time-periods following the same protocols. Results (1) Maternal cognitive capacities were positively related with child cognitive development early in life in more disadvantaged occupational social classes. (2) The levels of child cortisol were not related to child neuropsychological development during the second year of life. (3) Higher levels of long-chain polyunsaturated fatty acids in colostrum due to prolonged periods of breastfeeding improved early neuropsychological development of children, in particular in those children exposed to maternal smoking during pregnancy. (4) Prenatal exposure to PCBs (specially for PCB congener 153) impacted negatively on psychomotor development during the second year in life and on general neuropsychological development at the age of 4 years. (5) Postnatal exposure to organochlorine compounds was associated with a delay in reaction time (speed processing) during the preadolescent period. (6) The conceptual framework proposed will improve the quality of research in this area. Conclusions Social and cultural determinants such as maternal intelligence, educational level or occupational social class, are configuring the proximal environment in which a child develops and determine their neuropsychological development. Current levels of some organochlorine compounds, particularly polychlorinated byphenils, measured in blood samples (from umbilical cord, mothers, or children) are impairing on neuropsychological development in the general population. / Introducció El desenvolupament neuropsicològic infantil és un procés guiat genèticament, el qual és contínuament influenciat per factors socials i ambientals. L’objectiu d’aquesta tesis fou l’estudi dels principals determinants socio-ambientals del desenvolupament neuropsicològic infantil en diferents períodes de temps. Aquesta tesis també té l’objectiu de resumir en un marc conceptual els diferents components del desenvolupament neuropsicològic pel seu ús en estudis d’epidemiologia ambiental. Mètodes Aquesta tesis està basada en dades del projecte INMA (Infancia y Medio Ambiente). El principal objectiu d’aquest projecte és avaluar l’impacte de les exposicions ambientals en la salud infantil en 7 cohorts de població establides en diferents regions d’Espanya. Dintre del marc d’aquest projecte, s’ha avaluat el desenvolupament neuropsicològic d’aproximadament 2.650 nens en diferents moments, seguint els mateixos protocols. Resultats (1) Les capacitats cognitives maternes estan positivament relacionades amb el desenvolupament cognitiu infantil en les primeres etapes, en les classes socials ocupacionals menys afavorides. (2) Els nivells de cortisol infantil no mostren associació amb el desenvolupament neuropsicològic durant el segon any de vida. (3) Nivells elevats d’àcids grassos poliinsaturats de cadena llarga en conjunció amb períodes prolongats de lactancia materna afavoreixen el desenvolupament neuropsicològic a les primeres etapes, especialment en aquells nens de mares fumadores durant l’embaràs. (4) L’exposició prenatal a PCBs (espcialment, al congener 153) impacta negativament en el desenvolupament psicomotor infantil durant el segon any de vida i en el desenvolupament neuropsicològic general als 4 anys d’edat. (5) L’exposició postnatal a compostos organocloroats està associada a una capacitat de reacció (velocitat de processament) més alentida en etapes preadolescents. (6) L’ús del marc conceptual propossat tesis afavorirà la qualitat de l’investigació en aquesta àrea. Conclussions Els determinants socials, com l’intel•ligència materna, el nivell educatiu o la classe social basada en l’ocupació, configuren l’entorn més proper del nen i determinen el seu desenvolupament neuropsicològic. Els nivells actuals de certs compostos organoclorats, especialment els bifenils policlorinats, mesurats en mostres de sang (de cordó umbilical, mares o nens) mostren efectes negatius sobre el desenvolupament neuropsicològic en la població general. / Introducción El desarrollo neuropsicológico infantil es un proceso guiado genéticamente, el cual está contínuamente influenciado por factores sociales y ambientales. El objetivo de esta tesis fue estudiar los principales determinantes socio-ambientales del desarrollo neuropsicológico infantil en diferentes periodos de tiempo. Esta tesis también tenía como objetivo resumir en un marco conceptual el trabajo hecho en epidemiología ambiental en el estudio del desarrollo neuropsicológico infantil. Métodos Esta tesis está basada en datos del proyecto INMA (Infancia y Medio Ambiente). El principal objetivo de esto proyecto es evaluar el impacto de las exposiciones ambientales en la salud infantil en 7 cohortes de población establecidas en diferentes regiones de España. El desarrollo neuropsicológico de aproximadamente 2.650 niños ha sido evaluado en diferentes momentos siguiendo los mismos protocolos. Resultados (1) Las capacidades cognitivas maternas están positivamente relacionadas con el desarrollo cognitivo infantil en edades tempranas en las clases sociales ocupacionales menos aventajadas. (2) Los niveles de cortisol en el niño no se asocian con el desarrollo neuropsicológico durante el segundo año de vida. (3) Niveles altos de ácidos grasos poliinsaturados de cadena larga debido a periodos largos de lactancia materna mejoraron el desarrollo neuropsicológico a edades tempranas, especialmente en esos niños cuyas madres fumaron durante el embarazo. (4) La exposición prenatal a PCBs (espcialmente para el congener 153) impacta negativamente en el desarrollo psicomotor durante el segundo año de vida y en desarrollo neuropsicológico general a la edad de 4 años. (5) La exposición postnatal a compuestos organoclorados está asociado con una peor capacidad de tiempo de reacción (velocidad de procesamiento) durante la preadolescencia. (6) El marco conceptual propuesto mejorará la calidad de la investigación en esta área. Conclusiones Los determinantes sociales tales como inteligencia maternal, nivel educativo o clase social basada en la ocupación, configuran el entorno más cercano en el cual el niño se desarrolla y determinan su desarrollo neuropsicológico. Los niveles actuales de ciertos compuestos organoclorados, especialmente los bifeniles policlorinados, medidos en sangre (de cordón umbilical, madre, o niño) tienen efectos negativos sobre el desarrollo neuropsicológico de la población general.

O Pinguim-de-Magalhães, Spheniscus magellanicus, é o mais abundante dos pinguins que vivem em regiões temperadas da América do Sul, sendo um bom indicador de poluição ambiental. Poluentes orgânicos persistentes (POPs) foram detectados em fígado de Pinguins-de-Magalhães encontrados debilitados ou mortos nas praias do Brasil (Rio de Janeiro, São Paulo, Santa Catarina e Rio Grande do Sul) entre 2008 - 2012 e, do Uruguai e do Chile, em 2011. Os bifenilos policlorados (PCBs) predominaram em relação aos pesticidas organoclorados (DDTs ∼ HCB ∼ Drins) e aos éteres difenilos polibromados (PBDEs). O contaminante emergente fipronil não foi detectado apesar de seu uso na América do Sul. Entre os PCBs predominaram os congeneres penta, hexa e heptaclorados. Concentrações de POPs foram similares entre as áreas de migração e reprodução exceto para os PCBs que foram relativamente maiores na área de reprodução. Avaliação temporal (2008 - 2012) de POPs apresentou constância para os pesticidas organoclorados e tendência ao declínio para os PCBs. A glândula uropigiana de Pinguim-de-Magalhães mostrou-se um tecido alternativo adequado para análise de POPs em aves debilitadas. No geral, as regiões de reprodução e migração dos pinguins na América do Sul apresentam baixas concentrações de POPs com tendência constante ou indícios de declínio. / The Magellanic Penguin , Spheniscus magellanicus, is the most abundant penguin that live in temperate regions of South America and a good indicator of environmental pollution in that region. Persistent organic pollutants (POPs) were detected in the liver of Magellanic penguins found debilitated or dead on the beaches of Brazil (Rio de Janeiro, Sao Paulo, Santa Catarina and Rio Grande do Sul) between 2008 - 2012, and in Uruguay and Chile in 2011. Polychlorinated biphenyls (PCBs) were more prevalent than organochlorine pesticides (DDTs ∼ HCB ∼ Drins) and polybrominated diphenyl ethers (PBDEs). Fipronil, an emerging contaminant, was not detected despite its use in South America. Among PCBs, the congeners penta, hexa and heptaclorados were predominant. Concentrations of POPs are similar between the migration and reproduction areas except for PCBs that are relatively higher in the breeding area. At this time point (2008 - 2012) POPs showed constancy for organochlorine pesticides and PCBs tendency to decline. The Magellanic penguin uropygian gland has proved to be a suitable alternative for POPs tissue analysis in debilitated birds. Overall, southern South America has low concentrations of POPs with constant trend or decline evidence.

The polychlorinated biphenyls are synthetic organoclorated substances that can produce noxious effects to health. There are not any natural sources of PCBs known in the environment. They can be liquid or solid, colorless or clear yellow. Some of them are volatile and may remain as steams in the air. They were widely used in the industry as oils for transformers, electric capacitors, in transference fluids, inks, conservants for pesticides and lubricants, amongst others. Due to their inappropriate discard in the environment and also for the fact of presenting lingerence, bioaccumulation and high toxicity, they are distributed over the land surface, contaminating the alimentary chain. Victuals, mainly the most lipidic ones, such as the animal-originated products, have been recognized as the main source of PCBs ingestion. The concern about these compounds is in regard to their toxicological potential, mainly as cancer inductors. Milk and milk deriving products are an important source of macronutrients, with emphasis on proteins, vitamins, and mineral salts. Besides, they provide beneficial effects to health. Thus, the present dissertation has the purpose of investigating the existence of PCBs in integral powdered milk and to estimate the ingestion of these compounds from that victual by pre-scholars. Data of weight and consumption of powdered milk by children attending to infantile education schools of the municipal district of Imbé, RS, have been collected. The consumption of powdered milk among these children was of 32g per day, which is equivalent to 8,3g of daily fat. For the evaluation of the presence of PCBs 28, 52, 153, 138, and 180 in the powdered milk consumed by the pre-scholars we have proceeded the rebuilding of milk, followed by centrifugation in order to obtain the lipidic fraction. Subsequently, the lipidic content was extracted with sodium sulfate and ether of petroleum. The extraction and purification of the PCBs from fat were developed by using florisil and hexane. The identification and quantification of these compounds have been accomplished with the aid of the gas chromatograph equipped with micro electron capture detector (μECD). The confirmation was carried out on a gas chromatography coupled with mass spectrometer (GC/MS). The compounds concentrations were detected in the following order, from the most concentrated to the least concentrated: PCB 180 (0,157 ng g-1of fat) > PCB 138 (0,073 ng g-1) > PCB 28, 52 e 153 (<LQ). The PCB sum (PCB) was of 0,230 ng g-1of fat, oscillating from 0,000 to 2,857 ng g-1. The estimated daily ingestion of PCBs (PCBs) from powdered milk was of 0,0013 ng g-1 fat. This value, when compared with the reference limit admitted by the Brazilian legislation, is under the value established. On the basis of the results obtained it was possible to conclude that the milk consumed by the pre-scholars from PNAE of the municipal district of Imbé does not offer any toxicological risk. Nevertheless, it is suggested the importance of other works on this area with the purpose of monitoring the presence of residues of PCBs in milky products addressed to the infantile population once that they can generate adverse effects to health. / Os bifenilos policlorados são substâncias organocloradas sintéticas que podem causar efeitos lesivos à saúde. Não existem fontes naturais conhecidas de PCBs no ambiente. Eles podem ser líquidos ou sólidos, incolores ou amarelo claro. Alguns são voláteis e podem permanecer como vapores no ar. Foram amplamente utilizados na indústria como óleos para transformadores, capacitores elétricos, em fluídos de transferência, tintas, conservantes para pesticidas, lubrificantes e etc. Devido ao seu descarte inadequado no meio ambiente, e por apresentarem persistência, bioacumulação e grande toxicidade encontram-se distribuídos na superfície terrestre, contaminando a cadeia alimentar. Alimentos, especialmente os mais lipídicos, como os produtos de origem animal têm sido reconhecidos como a principal fonte de ingestão de PCBs. A preocupação quanto a estes compostos está voltada para o seu potencial toxicológico, principalmente como indutores de câncer. Leite e derivados lácteos, constituem uma importante fonte de macronutrientes, em especial as proteínas, vitaminas e sais minerais. Além disso, proporcionam efeitos benéficos à saúde. Diante do exposto, a presente dissertação tem como objetivo investigar a presença de PCBs em leite em pó integral e estimar a ingestão destes compostos a partir deste alimento por pré-escolares. Foram coletados os dados de peso e consumo de leite em pó por crianças matriculadas nas escolas de educação infantil no município de Imbé RS. O consumo de leite em pó pelas crianças foi de 32 g-1 dia, equivalente a 8,3 g de gordura/dia. Para avaliar a presença dos PCBs 28, 52, 153, 138 e 180 no leite em pó integral utilizado pelo Programa Nacional de Alimentação Escolar (PNAE) de Imbé e consumido pelos pré-escolares da rede de ensino municipal, procedeu-se a reconstituição do leite, seguido da centrifugação para obtenção da fração lipídica. Posteriormente, o conteúdo lipídico foi extraído com sulfato de sódio e éter de petróleo. A purificação e extração dos PCBs, a partir da gordura, foram feitas utilizando-se florisil e hexano. A identificação e a quantificação destes compostos foram feitas com auxílio de cromatógrafo a gás dotado de microdetector de captura de elétrons (μECD). A confirmação foi realizada por cromatógrafo a gás acoplado à espectrometria de massas (GC-MS). As concentrações dos compostos foram detectadas na seguinte ordem, do mais concentrado para o menos concentrados: PCB 180 (0,157 ng g-1 de gordura) > PCB 138 (0,073 ng g-1) > PCB 28, 53 e 153 (<LQ). O somatório de PCB (PCB) foi de 0,230 ng g-1 de gordura, variando de 0,000 a 2,857 ng g-1. A ingestão diária estimada de PCBs (PCBs), a partir de leite em pó, foi 0,0013 ng g-1 de gordura. Este valor, quando comparado com o limite de referência admitido pela legislação brasileira fica abaixo do valor estabelecido. Com base nos resultados obtidos, conclui-se que o leite consumido pelos pré-escolares do PNAE no município de Imbé não oferece risco toxicológico. No entanto, sugere-se a importância de outros trabalhos na área, com a finalidade de monitorar a presença de resíduos de PCBs em produtos lácteos destinado ao público infantil, uma vez que estes podem provocar efeitos adversos à saúde.

Foodstuffs free of toxic substances are a continuous concern, for food industry, educational and research institutes, and mainly for consumers. Polychlorinated biphenyls (PCBs) are industrial organochlorine substances used in electrical transformers and capacitors oil. Due to the inappropriate discharge, PCBs contaminate the environment and enter in the food chain, which constitutes main source for human contamination. Man, that is in the top of food chain, receives the higher levels of these compounds. The concern about PCBs is centered on its toxicological potential, mainly as cancer inductors. Thus, the present master dissertation is aimed at investigating PCBs residues in cheese and estimating the daily intake of these compounds from cheese. To investigate the intake of cheese and other animal food products by university students in Santa Maria, RS, a food consumption frequency questionnaire was used. It was observed that all surveyed students consume animal food products. Industrialized cheese intake was 99 g/week and homemade cheese was 22 g/week. To evaluate the levels of PCBs 10, 28, 52, 153, 138 and 180 in cheese produced in Rio Grande do Sul State; cheese fat was extracted using sodium sulfate and petroleum ether. PCBs clean-up was performed using florisil and hexane. The identification and quantification was made by a gas chromatography with microelectron capture detector (GC-μECD). PCBs were found in 94.7% of analyzed samples, in an average concentration of 30.84 ng/g fat (range 0.00 to 78.32 ng/g fat). The congener found at the highest concentration was PCB 52 (15.75 ng/g fat). Differences in PCB levels between industrialized (33.32 ng/g fat) and homemade (26.58 ng/g) cheese were not statistically significant (p>0.05). Similarly, no statistical difference was observed among the three regions evaluated: Mountain/Porto Alegre (36.21 ng/g fat); Santa Maria (27.64 ng/g) and South/ Western (26.61 ng/g). All samples evaluated exhibited contamination below the maximum PCB level allowed in European Community for dairy products (100 ng/g fat). Based on cheese consumption by university students, the estimated daily intake (EDI) of PCBs was 1.74 pg/kg body weight for industrialized cheese and 0.34 pg/kg for homemade cheese. The EDI is below the tolerable daily intake established by World Health Organization, that amounts 4% of IDT to homemade cheese and 22% of IDT to industrialized cheese, concluding that the cheese produced in Rio Grande do Sul not offer toxicological risk under the evaluated aspect. / Alimentos isentos de substâncias tóxicas são uma preocupação constante, tanto por parte das indústrias alimentícias, como das instituições de ensino e pesquisa, e principalmente dos consumidores. Os bifenilos policlorados (PCBs) são substâncias organocloradas que foram utilizadas na indústria em óleos para transformadores e capacitores elétricos. Devido ao seu descarte inadequado, poluem o meio ambiente e entram na cadeia alimentar, sendo esta a sua principal forma de contaminação humana. O homem, que ocupa os níveis tróficos mais elevados, recebe os maiores níveis destes compostos. A preocupação acerca dos PCBs está centrada no potencial toxicológico, principalmente como indutores de câncer. Neste contexto, a presente dissertação de mestrado tem como objetivo investigar a presença de PCBs em queijos e estimar a ingestão destes compostos a partir deste alimento. Para avaliar o consumo de queijo e outros produtos de origem animal por universitários de Santa Maria, RS, foi utilizado um questionário de freqüência de consumo de alimentos. Foi observado que todos os estudantes entrevistados consomem produtos de origem animal. O consumo de queijo industrializado foi de 99 g/semana e de queijo colonial foi de 22 g/semana. Para avaliar a presença dos PCBs 10, 28, 52, 153, 138 e 180 em queijos produzidos no Estado do Rio Grande do Sul, procedeu-se a extração da gordura com sulfato de sódio e éter de petróleo. A purificação dos PCBs a partir da gordura foi feita utilizando-se florisil e hexano. A identificação e quantificação destes compostos foi feita com auxílio de cromatógrafo gasoso dotado de microdetector de captura de elétrons. Os PCBs estavam presentes em 94,7% das amostras analisadas, em uma concentração média de 30,84 ng/g de gordura (intervalo de 0,00 78,32 ng/g). O congênere encontrado nas maiores concentrações foi o PCB 52 (15,75 ng/g de gordura). Também foi investigada a diferença dos níveis de PCBs nos queijos industrializado (33,32 ng/g de gordura) e colonial (26,58 ng/g), não tendo sido observada diferença significativa (p>0,05). Da mesma maneira, não foram observadas diferenças significativas nas três regiões avaliadas: Serra/Porto Alegre (36,21 ng/g de gordura), Santa Maria (27,64 ng/g) e Sul/Oeste (26,61 ng/g). Nenhuma amostra apresentou contaminação superior ao limite máximo permitido pela Comunidade Européia para produtos lácteos (100 ng/g de gordura). Com base no consumo de queijo pela população, observou-se que a ingestão diária estimada (IDE) de PCBs por universitários foi de 1,74 pg/kg de peso corporal para o queijo industrializado e 0,34 pg/kg para o queijo colonial. A IDE se encontra abaixo da ingestão diária tolerável (IDT) estabelecida pela Organização Mundial da Saúde, sendo de 4% da IDT para o queijo colonial e 22% da IDT para o queijo industrializado. Conclui-se que o queijo produzido no Rio Grande do Sul não oferece risco toxicológico sob o aspecto avaliado.

A tartaruga verde (Chelonia mydas) é uma tartaruga marinha que se alimenta e nidifica em locais da costa brasileira, ilhas e atóis. Esta espécie tem sido acometida pela fibropapilomatose (FP), doença considerada como uma das mais importantes ameaças à sua sobrevivência e caracterizada por tumores cutâneos benignos. A etiologia é multifatorial e complexa, possivelmente havendo relação entre Chelonid Fibropapilloma-associated Herpesvirus, fatores ambientais e genéticos. Foram estudadas 133 tartarugas verdes com e sem tumores provenientes de cinco áreas brasileiras: Florianópolis/SC, Ubatuba/SP, Vitória/ES, Almofala/CE e Fernando de Noronha/PE. Foram obtidos dados de biometria (comprimento curvilíneo da carapaça-CCC, massa corporal-MC e índice de condição corporal-ICC), tamanho (classificado por categorias A, B, C e D), quantidade e localização anatômica dos tumores, além da colheita de amostra sanguínea. Os objetivos foram (1) avaliar a atividade dos leucócitos por citometria de fluxo (fagocitose e burst oxidativo); (2) investigar a presença de sete congêneres de bifenilas policloradas (PCBs) e (3) estabelecer correlações entre PCBs e a atividade dos leucócitos. Houve diferenças no CCC entre tartarugas sem tumores de acordo com a área de estudo, na MC e no ICC entre animais acometidos ou não capturados em Ubatuba. Foram quantificados e classificados 1033 tumores de 50 tartarugas verdes, sendo que a quantidade por tartaruga variou de 1 a 61 e a maior parte foi classificada nas categorias de tamanho A (446 tumores) e B (520 tumores) e na região anterior (669 tumores). Foi observada diferença significativa nas concentrações do congênere PCB 138 entre tartarugas com e sem FP capturadas em Vitória. Animais acometidos tiveram maiores concentrações de todas as PCBs quantificadas, exceto as tartarugas verdes capturadas em Vitória no caso dos congêneres PCBs 118, 138, 153 e 180. PCB 138 foi quantificado em maior concentração nas amostras e PCB 180 em níveis menores. Não foram observadas correlações significativas entre concentrações de PCBs e atividade celular. A FP tem sido amplamente pesquisada e os estudos que visam estabelecer correlações entre poluentes químicos e saúde animal são extremamente importantes, pois podem contribuir para novas direções nos planos de ação para conservação. / The green sea turtle (Chelonia mydas) feeds and nests in Brazilian coast, islands and atolls. This species has been affected by fibropapillomatosis (FP), disease considered one of the most important threats to its survival and characterized by benign skin tumors. The etiology is multifactorial and complex, possibly having relation between Chelonid Fibropapilloma-associated Herpesvirus, environmental and genetic factors. Were studied 133 green sea turtles with and without FP from five Brazilian areas: Florianópolis/SC, Ubatuba/SP, Vitória/ES, Almofala/CE and Fernando de Noronha/PE. Were taken biometric data (curved carapace length-CCL, body mass-BM and body condition index-BCI), as well as size (classified by categories A, B, C and D), numbers and anatomical distribution of tumors, besides blood sample collection. The aims were (1) to assess leukocytes activity by flow cytometry (phagocytosis and oxidative burst); (2) to investigate the presence of seven congeners of polychlorinated biphenyls (PCBs) and (3) to establish correlations between PCBs and leukocytes activity. There were differences in CCL between turtles without FP according to the study area, in BM and BCI between affected and non-affected animals caught in Ubatuba. Were quantified and classified 1033 tumors of 50 green sea turtles, the number of tumors ranged from 1 to 61 and the most part of them was classified in categories of size A (446 tumors) and B (520 tumors) and in anterior region (669 tumors). Was observed difference in PCB 138 concentrations between green sea turtle with and without FP caught in Vitória. Affected animals had higher concentrations of all PCBs quantified, except green sea turtles caught in Vitória in the event of PCBs 118, 138, 153 and 180. Were quantified highest concentrations of PCB 138 and lowest of PCB 180. There were not significant correlations between PCBs concentration and leukocyte activity. The FP has been widely investigate and the studies that aimed to establish correlations between pollutants and animal health are very important, because can contribute for new directions in sea turtle conservation issues.

Orientadores: Helena Teixeira Godoy, Fabio Augusto / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-12T13:02:51Z (GMT). No. of bitstreams: 1 Kowalski_ClaudiaHoffmann_D.pdf: 1521730 bytes, checksum: 5077a83f5292bcd2dd1b651ce2fc229c (MD5) Previous issue date: 2008 / Resumo: Um estudo sobre a contaminação do leite materno com bifenilas policloradas (PCB) foi desenvolvido objetivando um conhecimento mais amplo dessa problemática no nosso país. Para isso, amostras de leite foram coletadas em nove estados brasileiros e questionários contendo perguntas sobre hábitos alimentares, condições sócio-econômicas, locais de habitação entre outras foram aplicados às mães doadoras. A determinação dos PCB foi feita por Microextração em Fase Sólida no modo headspace (HS-SPME) combinada com Cromatografia Gasosa e Detector de Captura de Elétrons (GC-ECD). As etapas da SPME foram otimizadas univariadamente e através de planejamento experimental Doehlert. A análise de variância mostrou que a temperatura de extração e a força iônica do meio (estudada através da adição de NaCl) foram as variáveis que mais influenciaram nas quantidades de PCB extraídas. Em seguida, refinaram-se as condições experimentais através de uma abordagem neuro-genética (rede neural Bayesiana aliada a algoritmos genéticos) que identificou como o ponto experimental ótimo a seguinte condição: concentração de NaCl de 0,36 g mL-1, temperatura de extração de 95,0 °C, tempo de extração de 60 minutos e adição de 210 µL de metanol. Após a otimização, o método foi validado através do estudo das figuras de mérito e apresentou-se linear na faixa estudada (1 a 16 µg L-1) com r > 0,9884, além de boa precisão (RSD < 12 %, n = 5), recuperação aceitável (71 a 127 %) e limites de quantificação entre 0,45 µg L-1 e 2,42 µg L-1. A fim de estabelecer correlações entre os resultados das amostras (expressos na forma de áreas cromatográficas) e os resultados obtidos nos questionários, fez-se uso da rede neural de Kohonen. Assim, foi possível verificar que nas cidades metropolitanas o acúmulo de PCB no leite é mais expressivo que em outras regiões. Por exemplo, em São Paulo 58 % das amostras estavam contaminadas com algum PCB, principalmente os congêneres 180 e 153. Outro resultado gerado pela rede foi que, em geral, as amostras de leite maduro (maior porcentagem de gordura) estavam mais contaminadas com PCB. O número de gestações também foi um fator importante a ser considerado, pois o estudo mostrou que o primeiro filho normalmente recebe uma dose maior de PCB do que os demais. Ainda, maior contaminação foi encontrada no leite de mães que moram nas proximidades de indústrias e/ou rios poluídos, corroborando com o fato de que esses compostos chegam facilmente ao meio ambiente e em seguida aos seres humanos / Abstract: A study about the contamination of the breast milk with polychlorinated biphenyls (PCB) was developed aiming a wider knowledge of this problematic in our country. For that, breast milk samples were collected in nine Brazilian states and questionnaires with questions regarding to food habits, social and economic conditions, places of dwelling between others were applied to the donors. The determination of the PCB was done by headspace Solid-Phase Microextraction (HS-SPME) combined with Gas Chromatography and Electron Capture Detector (GC-ECD). The SPME steps were optimized through univariated procedures and Doehlert experimental design. The analysis of variance showed that the temperature of extraction and the ionic strength of the media (studied by the addition of NaCl) were the most significant variables in the quantities of extracted PCB. After that, the experimental conditions were refined considering a neurogenetic approach (Bayesian neural network and genetic algorithms) and it was identified as the optimum experimental point the following condition: concentration of NaCl of 0.36 g mL-1, temperature of extraction of 95.0 °C, time of extraction of 60 minutes and addition of 210 µL of methanol. After the optimization, the method was validated through the study of the figures of merit. It showed linear in the studied range (1 to 16 µg L-1) with r > 0.9884, besides good precision (RSD < 12 %, n = 5), acceptable recuperation (71 to 127 %) and limits of quantization between 0.45 µg L-1 and 2.42 µg L-1. In order to establish correlations between the results of the samples (expressed as chromatographic areas) and the results obtained in the questionnaires, Kohonen neural network had been used. Thus, it was possible to check that in the metropolitan cities the accumulation of PCB in the milk is more expressive than in other regions. For example, in Sao Paulo state, 58 % of the samples were contaminated by some PCB, mainly the congener 180 and 153. Another result produced by the net was that the samples of hindmilk (higher fat percentage) were the most contaminated. The number of gestations also was an important factor to be considered, since the study showed that the first son normally receives a higher dosage of PCB compared to the others. Also higher levels of contamination was found in the milk of mothers who lived in the proximities of industries and/or polluted rivers, corroborating with the fact that these compounds are easily spread in the environment and consequently in the human beings / Doutorado / Doutor em Ciência de Alimentos