This thesis is concerned with the fate of hydrophobic organic pollutants (HOCs) in soil. The theoretical part summarizes the current knowledge about bioavailability, factors influencing the bioavailability and methods for its measurement. Attention is paid to the organic carbon content, which is considered to be one of the key factors and to the influence of microorganisms that can degrade or interact with the substances, thus changing their bioavailable ratio. The practical part of the thesis uses bioaccumulation test with earthworm Eisenia andrei for evaluating the uptake kinetics HOCs in three soils with different organic carbon content. Soils were laboratory contaminated with mixtures of selected HOCs (phenanthrene, pyrene, lindane, p,p'-DDT and PCB 153) and the concentrations of substances in these soils were followed for 217 days. Subsequently, bioaccumulation test was conducted; earthworms were exposed from one to twenty-one days. The collected data were used to model uptake kinetics curves for individual substances. Peak-shaped bioaccumulation were found for pyrene, for lindane a steady-state concentration during exposure was observed, whereas for p,p'-DDT and PCB 153 growing concentrations after twenty days of exposure were detected. The reason for the different behavior of the substances was probably their diverse sorption on the organic material, which together with the different speed of elimination influenced final concentration in earthworms. Phenanthrene was not detected in some samples and therefore the modeling of uptake kinetics was not possible.

The ability of Chromolaena odorata propagated by stem cuttings and grown for six weeks in the greenhouse to thrive in soil containing different concentrations of PCB congeners found in Aroclor and transformer oil, and to possibly remediate such soil was studied under greenhouse conditions. Chromolaena odorata plants were transplanted into soil containing 100, 200, and 500 ppm of Aroclor and transformer oil (T/O) in 1L pots. The experiments were watered daily at 70% moisture field capacity. Parameters such as mature leaves per plant, shoot length, leaf colour as well as the root length at harvest were measured. C. odorata growth was negatively affected by T/O in terms of shoot length and leaf numbers, but no growth inhibition was shown by Aroclor. At the end of six weeks of growth, Plants size was increased by 1.4 and 0.46%, but decreased at -1.0% in T/O, while increases of 45.9, 39.4 and 40.0% were observed in Aroclor treatments. Mean total PCB recoveries were 6.40, 11.7, and 55.8μg in plants tissues at Aroclor treated samples resulting in a percentage reduction of PCB from the soil to 2.10, 1.50, and 1.10 at 100, 200, and 500mg/kg Aroclor treatments respectively. There was no PCB recovery from plants in transformer oil treatments as a result of its inhibition to growth. Root uptake was found to be the probable means of remediation of PCB-contaminated soil by C. odorata, this was perhaps aided by microbes. This study has provided evidence on the ability of C. odorata to remediate PCB contaminated soil. However, the use of C. odorata for phytoremediation of PCB contaminated soil under field condition is therefore advised. / Environmental Sciences / M.Sc. (Environmental Science)

Poly- and perfluoroalkyl substances (PFAS) are ubiquitous contaminants across the globe, can bioaccumulate in aquatic taxa, and potentially biomagnify in food webs. Consequently, research examining the influence of PFAS on wildlife is warranted. Amphibians are sensitive to contaminants such as PFAS because of their porous skin and associations with aquatic habitats where contaminants accumulate. Because PFAS tend to bioaccumulate and can adversely affect the endocrine system, there is a need to examine uptake rates to inform ecotoxicology studies, as well as a need to examine sublethal effects. To address these knowledge gaps I conducted two experiments. First, I exposed larval northern leopard frogs (<i>Rana pipiens</i>), American toads (<i>Anaxyrus americanus</i>), and eastern tiger salamanders (<i>Ambystoma tigrinum</i>) to PFAS chemicals perfluorooctanoic acid (PFOA) or perfluorooctane sulfonate (PFOS) at concentrations of 10 or 1000 ppb for 10 days and sampled them every 48 hours during the exposure period. In the next experiment, I examined the effects of PFAS exposure via contaminated substrate on the survival and growth of post metamorphic amphibians of the same species. I found that, for all species, body burdens often reached steady state within 48 to 96 h of exposure. Steady-state body burdens of PFOA ranged from 3,819–16,481 ng/g dry weight among treatments and species (corresponding BCFs of 0.5 to 2.5), while PFOS body burdens ranged from 6,955–489,958 ng/g dry weight (corresponding BCFs of 47–259) among treatments and species. These data suggest that steady state is rapidly reached in larval amphibians exposed to PFAS, particularly regarding PFOS. This reflects a high potential for trophic transfer of PFAS within food webs because amphibians are often low in trophic position and are important prey for many aquatic and terrestrial species. In post-metamorphic amphibians, there was no influence of PFAS on survival or mass. However, significant effects on snout-vent length were observed in all species, and body condition differences were observed for two of my species. I found that all leopard frogs increased in scaled mass index (SMI) when exposed to a PFAS treatment, indicating an increased body condition. Toads exhibited a more variable SMI pattern across treatments, with no outstanding trends, and tiger salamanders did not differ significantly across treatments. These data suggest that sublethal effects vary greatly depending on the species, possibly due to life history traits. Future research examining biomagnification potential is warranted to determine the influence of PFAS on food webs. Additionally, there is a need to determine the physiological mechanisms underlying the observed effects of PFAS exposure.<br>

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-10-04T15:44:46Z No. of bitstreams: 1 tese_renata_maria_completa.pdf: 1532064 bytes, checksum: db3c7a043c5eecc779b264a3e956dea2 (MD5) / Made available in DSpace on 2017-10-04T15:44:46Z (GMT). No. of bitstreams: 1 tese_renata_maria_completa.pdf: 1532064 bytes, checksum: db3c7a043c5eecc779b264a3e956dea2 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Nos últimos anos observa-se um aumento crescente das atividades humanas, tanto científicas quanto turísticas, no ambiente antártico, sendo motivo de preocupação considerando-se que a Antártica é um ambiente de lenta recuperação. Ainda são escassos os estudos sobre o estabelecimento de relações entre a presença de contaminantes e seus efeitos na biota antártica. A contaminação pode ocorrer por processos antrópicos ou naturais e os efeitos destes impactos podem ser detectados e monitorados através da análise das alterações nas comunidades bentônicas. Estas comunidades podem ser consideradas boas indicadoras de impactos ambientais, já que possuem uma relação direta com a origem dos contaminantes acumulados nos sedimentos. Este trabalho avaliou os níveis de metais-traço encontrados no sedimento e em duas espécies circumpolares da megafauna bentônica antártica, a estrela-domar Odontaster validus e o molusco bivalve Laternula elliptica, com a finalidade de determinar se as mesmas podem ser utilizadas como indicadoras de impacto ambiental. Durante o verão austral de 2005/2006 foram realizadas coletas através de diferentes procedimentos, entre 15 e 40m de profundidade, em cinco estações dentro da Área Antártica Especialmente Gerenciada da Baía do Almirantado, Ilha Rei George: 1) Estação Antártica Comandante Ferraz; 2) Botany Point; 3) Punta Ullman; 4) Punta Plaza e 5) Refúgio II. Os seguintes metais foram quantificados tanto para o sedimento quanto para os organismos: Al, V, Cr, Mn, Fe, Ni, Cu, Cd, Ba, Pb e Zn. A concentração de metais variou entre os diferentes compartimentos corpóreos analisados. Para a espécie O. validus, as maiores concentrações de metais-traço (Mn, Ni, Cd, Ba, Pb) e do macronutriente Al, foram encontradas na parede do corpo. Cu, Cr, V e Zn apresentaram maior concentração no estômago, enquanto o macronutriente Fe concentrou-se preferencialmente nos cecos pilóricos. Para a espécie L. elliptica, as maiores concentrações de metais-traço (Mn, V, Ba, Cu) e dos macronutrientes Fe e Al, foram encontradas no sifão. Cd, Ni, Pb e Zn apresentaram maior concentração no rim enquanto o Cr foi mais concentrado no compartimento restos. A concentração de elementostraço nos compartimentos corpóreos de O. validus e L. elliptica não foi influenciada pelo tamanho do organismo (peso total do indivíduo). / Once the Antarctic environment has low recovery rates, the recent growth in the touristic and scientific activities is a serious issue for the scientific community. Few studies have tried to establish the links between the presence of contaminants and the antarctic biota. The contamination may be related to human or natural processes, and be monitored trough the benthic communities. These communities have a direct relation with the contaminants sources in the sediment. The present work analyzed the trace-metals levels found in the sediment and two circumpolar benthic megafauna species in Antarctica, the starfish Odontaster validus and the Antarctic clam Laternula elliptica. The objective was to establish if these species can be used as environmental indicators. Five stations was occupied during the austral summer of 2005/2006, between 15 and 40m deep, in the Antarctic Special Management Area of Admiralty Bay, George King Island: 1) Comandante Ferraz Antarctic Base; 2) Botany Point; 3) Punta Ullman; 4) Punta Plaza and 5) Refúgio II. Analyzes were conducted to quantify the presence of Al, V, Cr, Mn, Fe, Ni, Cu, Cd, Ba, Pb and Zn, both in the sediment and organisms. The metals concentrations vary in the different body compartments. Larger concentrations of (Mn, Ni, Cd, Ba, Pb) trace metals and Al macronutrient were found in the body walls of O. validus. Cu, Cr, V and Zn showed larger concentrations in the stomach and the Fe macronutrient in the caeca pyloric. For L. elliptica, larger trace metals (Mn, V, Ba, Cu) and macronutrients (Fe and Al) concentrations were found in the sifon, while Cd, Ni, Pb and Zn showed larger concentrations in the kidney. Cr presented larger concentrations in the remains compartment. The concentrations of trace elements in both O. validus and L. elliptica were not influenced by the body size (total individual weight).

The ability of Chromolaena odorata propagated by stem cuttings and grown for six weeks in the greenhouse to thrive in soil containing different concentrations of PCB congeners found in Aroclor and transformer oil, and to possibly remediate such soil was studied under greenhouse conditions. Chromolaena odorata plants were transplanted into soil containing 100, 200, and 500 ppm of Aroclor and transformer oil (T/O) in 1L pots. The experiments were watered daily at 70% moisture field capacity. Parameters such as mature leaves per plant, shoot length, leaf colour as well as the root length at harvest were measured. C. odorata growth was negatively affected by T/O in terms of shoot length and leaf numbers, but no growth inhibition was shown by Aroclor. At the end of six weeks of growth, Plants size was increased by 1.4 and 0.46%, but decreased at -1.0% in T/O, while increases of 45.9, 39.4 and 40.0% were observed in Aroclor treatments. Mean total PCB recoveries were 6.40, 11.7, and 55.8μg in plants tissues at Aroclor treated samples resulting in a percentage reduction of PCB from the soil to 2.10, 1.50, and 1.10 at 100, 200, and 500mg/kg Aroclor treatments respectively. There was no PCB recovery from plants in transformer oil treatments as a result of its inhibition to growth. Root uptake was found to be the probable means of remediation of PCB-contaminated soil by C. odorata, this was perhaps aided by microbes. This study has provided evidence on the ability of C. odorata to remediate PCB contaminated soil. However, the use of C. odorata for phytoremediation of PCB contaminated soil under field condition is therefore advised. / Environmental Sciences / M.Sc. (Environmental Science)

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