Sorption of non-ionic organic compounds to organic matter is usually characterized as a partitioning interaction, which is quantified by K [subscript]oc, the organic-C normalized partitioning coefficient. However K [subscript]oc for any single compound varies considerably between soils, often by a factor of 3-10. This study addresses some of the potential causes of this variability. Forty-four soil cores were collected from a 2 ha paddock. Ten of these cores were selected for sorption measurements. The chemical composition of the soil organic matter (SOM) was determined using ¹³C NMR analysis. It was found that K [subscript]oc for diuron was positively correlated with aryl C (r² = 0.59) and negatively correlated with O-alkyl C (r² = 0.84). There were no such correlations for phenanthrene K [subscript]oc. A second set of experiments was carried out to investigate the effects of SOM– mineral interactions on the sorption properties of a selection of the soils. It was found that HF-treatment increased K [subscript]oc for both phenanthrene and diuron. The HF treatment removes mineral matter leaving the organic phase unaffected by the treatment. The increase in K [subscript]oc on HF-treatment soils provides strong evidence that interactions between organic matter and soil minerals block organic matter sorption sites. Furthermore, following HF-treatment, there was a positive correlation between K [subscript]oc for phenanthrene and aryl C and carbonyl C and a negative correlation with O-alkyl C. This suggests that the non-constancy of the relationship between organic matter chemistry and K [subscript]oc, for whole soils in the case of phenanthrene, may be a consequence of variability of the effect of organic matter-mineral interactions on K [subscript]oc. The influence of lipids on the sorption of diuron and phenanthrene to soils was also investigated. Lipids are known to cover the surfaces of organic matter in soil. K [subscript]oc for diuron and phenanthrene were consistently higher for the lipid-extracted soils than for the whole soils (average of 31% for diuron and 29% for phenanthrene), indicating that lipids block sorption sites on the organic matter. Sorption experiments on one pair of HF-treated soils indicated that the blocking effects of minerals and lipids are independent, because lipid extraction and HF-treatment combined increased K [subscript]oc by more than either treatment alone. In the last experiment, the effect of solvent conditioning on the sorption of diuron and phenanthrene was investigated. The K [subscript]oc values for compounds were consistently higher for solvent-treated whole soil and lipid-extracted soil than corresponding soils before solvent treatment. Solid-state ¹³C NMR spectra of the solvent-treated soils indicated that there were no significant changes in the chemical structure of SOM caused by solvent treatment. Solvent treatment changes the physical conformation of the SOM, increasing its sorption affinity. The key findings from the research are: • Variations in sorption affinity for diuron are related to differences in the soil organic matter chemistry. • SOM-mineral interactions can have a substantial influence on K [subscript]oc for non- ionic compounds. • Lipids may block the active sorption sites on the SOM thereby diminishing sorption overall. • Solvent conditioning can change the physical conformation of SOM and lead to enhancement sorption of diuron and phenanthrene. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1372068 / Thesis (Ph.D.) - University of Adelaide, School of Earth and Environmental Sciences, 2009

Sorption of non-ionic organic compounds to organic matter is usually characterized as a partitioning interaction, which is quantified by K [subscript]oc, the organic-C normalized partitioning coefficient. However K [subscript]oc for any single compound varies considerably between soils, often by a factor of 3-10. This study addresses some of the potential causes of this variability. Forty-four soil cores were collected from a 2 ha paddock. Ten of these cores were selected for sorption measurements. The chemical composition of the soil organic matter (SOM) was determined using ¹³C NMR analysis. It was found that K [subscript]oc for diuron was positively correlated with aryl C (r² = 0.59) and negatively correlated with O-alkyl C (r² = 0.84). There were no such correlations for phenanthrene K [subscript]oc. A second set of experiments was carried out to investigate the effects of SOM– mineral interactions on the sorption properties of a selection of the soils. It was found that HF-treatment increased K [subscript]oc for both phenanthrene and diuron. The HF treatment removes mineral matter leaving the organic phase unaffected by the treatment. The increase in K [subscript]oc on HF-treatment soils provides strong evidence that interactions between organic matter and soil minerals block organic matter sorption sites. Furthermore, following HF-treatment, there was a positive correlation between K [subscript]oc for phenanthrene and aryl C and carbonyl C and a negative correlation with O-alkyl C. This suggests that the non-constancy of the relationship between organic matter chemistry and K [subscript]oc, for whole soils in the case of phenanthrene, may be a consequence of variability of the effect of organic matter-mineral interactions on K [subscript]oc. The influence of lipids on the sorption of diuron and phenanthrene to soils was also investigated. Lipids are known to cover the surfaces of organic matter in soil. K [subscript]oc for diuron and phenanthrene were consistently higher for the lipid-extracted soils than for the whole soils (average of 31% for diuron and 29% for phenanthrene), indicating that lipids block sorption sites on the organic matter. Sorption experiments on one pair of HF-treated soils indicated that the blocking effects of minerals and lipids are independent, because lipid extraction and HF-treatment combined increased K [subscript]oc by more than either treatment alone. In the last experiment, the effect of solvent conditioning on the sorption of diuron and phenanthrene was investigated. The K [subscript]oc values for compounds were consistently higher for solvent-treated whole soil and lipid-extracted soil than corresponding soils before solvent treatment. Solid-state ¹³C NMR spectra of the solvent-treated soils indicated that there were no significant changes in the chemical structure of SOM caused by solvent treatment. Solvent treatment changes the physical conformation of the SOM, increasing its sorption affinity. The key findings from the research are: • Variations in sorption affinity for diuron are related to differences in the soil organic matter chemistry. • SOM-mineral interactions can have a substantial influence on K [subscript]oc for non- ionic compounds. • Lipids may block the active sorption sites on the SOM thereby diminishing sorption overall. • Solvent conditioning can change the physical conformation of SOM and lead to enhancement sorption of diuron and phenanthrene. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1372068 / Thesis (Ph.D.) - University of Adelaide, School of Earth and Environmental Sciences, 2009

Sorption of non-ionic organic compounds to organic matter is usually characterized as a partitioning interaction, which is quantified by K [subscript]oc, the organic-C normalized partitioning coefficient. However K [subscript]oc for any single compound varies considerably between soils, often by a factor of 3-10. This study addresses some of the potential causes of this variability. Forty-four soil cores were collected from a 2 ha paddock. Ten of these cores were selected for sorption measurements. The chemical composition of the soil organic matter (SOM) was determined using ¹³C NMR analysis. It was found that K [subscript]oc for diuron was positively correlated with aryl C (r² = 0.59) and negatively correlated with O-alkyl C (r² = 0.84). There were no such correlations for phenanthrene K [subscript]oc. A second set of experiments was carried out to investigate the effects of SOM– mineral interactions on the sorption properties of a selection of the soils. It was found that HF-treatment increased K [subscript]oc for both phenanthrene and diuron. The HF treatment removes mineral matter leaving the organic phase unaffected by the treatment. The increase in K [subscript]oc on HF-treatment soils provides strong evidence that interactions between organic matter and soil minerals block organic matter sorption sites. Furthermore, following HF-treatment, there was a positive correlation between K [subscript]oc for phenanthrene and aryl C and carbonyl C and a negative correlation with O-alkyl C. This suggests that the non-constancy of the relationship between organic matter chemistry and K [subscript]oc, for whole soils in the case of phenanthrene, may be a consequence of variability of the effect of organic matter-mineral interactions on K [subscript]oc. The influence of lipids on the sorption of diuron and phenanthrene to soils was also investigated. Lipids are known to cover the surfaces of organic matter in soil. K [subscript]oc for diuron and phenanthrene were consistently higher for the lipid-extracted soils than for the whole soils (average of 31% for diuron and 29% for phenanthrene), indicating that lipids block sorption sites on the organic matter. Sorption experiments on one pair of HF-treated soils indicated that the blocking effects of minerals and lipids are independent, because lipid extraction and HF-treatment combined increased K [subscript]oc by more than either treatment alone. In the last experiment, the effect of solvent conditioning on the sorption of diuron and phenanthrene was investigated. The K [subscript]oc values for compounds were consistently higher for solvent-treated whole soil and lipid-extracted soil than corresponding soils before solvent treatment. Solid-state ¹³C NMR spectra of the solvent-treated soils indicated that there were no significant changes in the chemical structure of SOM caused by solvent treatment. Solvent treatment changes the physical conformation of the SOM, increasing its sorption affinity. The key findings from the research are: • Variations in sorption affinity for diuron are related to differences in the soil organic matter chemistry. • SOM-mineral interactions can have a substantial influence on K [subscript]oc for non- ionic compounds. • Lipids may block the active sorption sites on the SOM thereby diminishing sorption overall. • Solvent conditioning can change the physical conformation of SOM and lead to enhancement sorption of diuron and phenanthrene. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1372068 / Thesis (Ph.D.) - University of Adelaide, School of Earth and Environmental Sciences, 2009

Sorption of non-ionic organic compounds to organic matter is usually characterized as a partitioning interaction, which is quantified by K [subscript]oc, the organic-C normalized partitioning coefficient. However K [subscript]oc for any single compound varies considerably between soils, often by a factor of 3-10. This study addresses some of the potential causes of this variability. Forty-four soil cores were collected from a 2 ha paddock. Ten of these cores were selected for sorption measurements. The chemical composition of the soil organic matter (SOM) was determined using ¹³C NMR analysis. It was found that K [subscript]oc for diuron was positively correlated with aryl C (r² = 0.59) and negatively correlated with O-alkyl C (r² = 0.84). There were no such correlations for phenanthrene K [subscript]oc. A second set of experiments was carried out to investigate the effects of SOM– mineral interactions on the sorption properties of a selection of the soils. It was found that HF-treatment increased K [subscript]oc for both phenanthrene and diuron. The HF treatment removes mineral matter leaving the organic phase unaffected by the treatment. The increase in K [subscript]oc on HF-treatment soils provides strong evidence that interactions between organic matter and soil minerals block organic matter sorption sites. Furthermore, following HF-treatment, there was a positive correlation between K [subscript]oc for phenanthrene and aryl C and carbonyl C and a negative correlation with O-alkyl C. This suggests that the non-constancy of the relationship between organic matter chemistry and K [subscript]oc, for whole soils in the case of phenanthrene, may be a consequence of variability of the effect of organic matter-mineral interactions on K [subscript]oc. The influence of lipids on the sorption of diuron and phenanthrene to soils was also investigated. Lipids are known to cover the surfaces of organic matter in soil. K [subscript]oc for diuron and phenanthrene were consistently higher for the lipid-extracted soils than for the whole soils (average of 31% for diuron and 29% for phenanthrene), indicating that lipids block sorption sites on the organic matter. Sorption experiments on one pair of HF-treated soils indicated that the blocking effects of minerals and lipids are independent, because lipid extraction and HF-treatment combined increased K [subscript]oc by more than either treatment alone. In the last experiment, the effect of solvent conditioning on the sorption of diuron and phenanthrene was investigated. The K [subscript]oc values for compounds were consistently higher for solvent-treated whole soil and lipid-extracted soil than corresponding soils before solvent treatment. Solid-state ¹³C NMR spectra of the solvent-treated soils indicated that there were no significant changes in the chemical structure of SOM caused by solvent treatment. Solvent treatment changes the physical conformation of the SOM, increasing its sorption affinity. The key findings from the research are: • Variations in sorption affinity for diuron are related to differences in the soil organic matter chemistry. • SOM-mineral interactions can have a substantial influence on K [subscript]oc for non- ionic compounds. • Lipids may block the active sorption sites on the SOM thereby diminishing sorption overall. • Solvent conditioning can change the physical conformation of SOM and lead to enhancement sorption of diuron and phenanthrene. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1372068 / Thesis (Ph.D.) - University of Adelaide, School of Earth and Environmental Sciences, 2009

The persistent organic pollutants (POPs) refer to many different chemicals that, upon release into the environment, remain intact for several decades. These contaminants travel long distances through repeated cycles of deposition and evaporation, and eventually deposit in the Arctic regions. The purpose of this work was to examine the potential human health implications of POP exposures among the Canadian Inuit, using modelling and epidemiological approaches. Blood guideline values were developed for the organochlorine pesticides, chlordane and toxaphene, and the polychlorinated biphenyls (PCBs) using the concept of biomonitoring equivalents (BEs), which are based on toxicity endpoints and toxicokinetic modelling to convert an oral reference dose to an equivalent blood concentration. The biomonitoring data from the Adult Inuit Health Survey (2007-2008) and the Canadian Health Measures Survey (CHMS, Cycle 1 2007-2009) were compared with the derived guideline values to assess population-level risks of exposures for the Inuit and the general Canadian population, respectively. Epidemiological analyses were also conducted to explore if POPs were associated with diabetes and high cholesterol, using data from the Inuit Health Survey. A set of BE values were derived for chlordane isomers and metabolite, three abundant toxaphene isomers, and the PCBs. The derived values are in a similar range of the BEs of other POPs in the literature. Among the Inuit, a large percentage exceeded the trans-nonachlor guideline value, particularly among the elderly. Fewer exceedances were observed for cis-nonachlor and oxychlordane, none for toxaphene, and minimally for the PCBs. In comparison, no exceedances for any of the POPs were observed in the general Canadian population. Highest vs. lowest quartile exposures to PCBs and p,p’-DDE were associated with increased risk of diabetes and an increase in fasting glucose among the Inuit. In addition, PCBs were associated with increased risk of high cholesterol, and higher levels of serum triglycerides, total cholesterol, and low-density lipoprotein cholesterol (LDL-C), but not high-density lipoprotein cholesterol (HDL-C). The results of this work suggest that exposures to POPs remain a potential health concern among the Canadian Inuit. Future research efforts should be devoted to collecting updated contaminant concentrations for the Inuit, measuring contaminants in prepared food samples, conducting cohort studies on contaminant exposures and health outcomes, and assessing the effects of chemical mixtures using statistical approaches and toxicokinetic modelling.

Otter populations declined drastically across many areas of England and Wales during the 1960s to 1980s. The main cause of this decline is thought to have been high concentrations of organic pollutants, in particular PCBs and dieldrin. Here we look at the health of the present day otter population, focussing on the numbers of otters, the genetic diversity of populations and investigating a possible new organic pollutant threat, polybrominated diphenyl ethers (PBDEs). A non-invasive spraint genotyping study of the otter population inhabiting the River Camel in Cornwall not only revealed that the river was capable of supporting a minimum number of 12 otters over a 9 month period, but gave insight into the ranges and genetic relationships of the individuals using the river system. A further population genetic study was carried out focussing on the River Itchen in Hampshire, a population which declined drastically to just a few isolated individuals before receiving otters through a captive breeding programme. Microsatellite genotyping of tissue samples showed the River Itchen population to be relatively diverse, indicating a successful population recovery, and haplotype analysis reveals that captive bred otters have successfully bred within the River Itchen population. However, haplotype analysis also indicates that the otters used to found the captive breeding programme were unlikely to have originated from a native British population. Concentrations of PBDEs in otters rival the high concentrations observed in many marine mammal species and are approaching the concentrations of PCBs and DDTs already observed in otters. The profile of the PBDE congeners found shows that lower congeners show relative concentrations similar to those observed in many other species of biota, with high BDE-47 dominating the profile and BDE-99 and -100 also found at significant concentrations. Otters also contain relatively high concentrations of the congeners BDE-153 and BDE-209, a trend generally typical of terrestrial top predators. In summary, the otter populations studied appear to be recovering well. However, increasing concentrations of PBDEs may cause problems for otter populations in the future.

Chemical species carry information in two dimensions, in their concentrations and their isotopic signatures. The concentrations of metabolites or synthetic compounds describe the composition of a chemical or biological system, while isotopic signatures describe processes in the system by their reaction pathways, regulation, and responses to external stimuli. Stable isotopes are unique tracers of these processes because their natural abundances are modulated by isotope effects occurring in physical processes as well as in chemical reactions. Nuclear magnetic resonance (NMR) spectroscopy is a prime technique not only for identification and quantification of small molecules in complex systems but also for measuring intramolecular distribution of stable isotopes in metabolites and other small molecules. In this thesis, we use quantitative NMR in three fields: in food science, environmental pollutant tracing, and plant-climate science. The phospholipid (PL) composition of food samples is of high interest because of their nutritional value and technological properties. However, the analysis of PLs is difficult as they constitute only a small fraction of the total lipid contents in foods. Here, we developed a method to identify PLs and determine their composition in food samples, by combining a liquid-liquid extraction approach for enriching PLs, with specialized 31P,1H-COSY NMR experiments to identify and quantify PLs. Wide-spread pollution with synthetic compounds threatens the environment and human health. However, the fate of pollutants in the environment is often poorly understood. Using quantitative deuterium NMR spectroscopy, we showed for the nitrosamine NDMA and the pesticide DDT how intramolecular distributions (isotopomer patterns) of the heavy hydrogen isotope deuterium reveal mechanistic insight into transformation pathways of pollutants and organic compounds in general. Intramolecular isotope distributions can be used to trace a pollutant’s origin, to understand its environmental transformation pathways and to evaluate remediation approaches. The atmospheric CO2 concentration ([CO2]) is currently rising at an unprecedented rate and plant responses to this increase in [CO2] influence the global carbon cycle and will determine future plant productivity. To investigate long-term plant responses, we developed a method to elucidate metabolic fluxes from intramolecular deuterium distributions of metabolites that can be extracted from historic plant material. We show that the intramolecular deuterium distribution of plant glucose depends on growth [CO2] and reflects the magnitude of photorespiration, an important side reaction of photosynthesis. In historic plant samples, we observe that photorespiration decreased in annual crop plants and natural vegetation over the past century, with no observable acclimation, implying that photosynthesis increased. In tree-ring samples from all continents covering the past 60 – 700 years, we detected a significantly smaller decrease in photorespiration than expected. We conclude that the expected “CO2 fertilization” has occurred but was significantly less pronounced in trees, due to opposing effects. The presented applications show that intramolecular isotope distributions not only provide information about the origin and turnover of compounds but also about metabolic regulation. By extracting isotope distributions from archives of plant material, metabolic information can be obtained retrospectively, which allows studies over decades to millennia, timescales that are inaccessible with manipulation experiments.

Many of the factors that shape contaminant accumulation profiles in marine mammals also strongly influence fat soluble vitamin accumulation. Vitamin A and E are essential fat soluble nutrients for numerous biological processes, including reproduction, growth, endocrine and immune function. Contaminants, such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), can alter vitamin dynamics; as such these vitamins have been proposed as sensitive biomarkers of contaminant exposure in wildlife. In light of these considerations, the present thesis was aimed at better understanding the factors that influence the accumulation of lipophilic contaminants and vitamins in western Arctic beluga whales, and to determine if there was an interaction between the two. Maternal offloading to neonates during gestation reduced overall contaminant (PCBs and PBDEs) and vitamin (A and E) concentrations in reproductively active female whales. The PCB and PBDE congener pattern in mothers changed during gestation as a result of preferential transfer of light-low Log KOW congeners to the fetus. Overall, female beluga whales transferred approximately 11% of their PCB and PBDE blubber burden to their fetus. In terms of vitamins transfer, lower concentrations of tocopherols, retinol and retinyl esters were found in reproductively active females relative to males and reproductively inactive females. Metabolism was also found to be an important factor for contaminant and vitamin accumulation in beluga tissues. In a principal components analysis, PCBs clustered into metabolically-derived structure-activity groups, which separated along the first principal component according to its metabolic potential (metabolizable vs. recalcitrant). Contaminant-related up-regulation of metabolizing enzymes, including cytochrome P450, likely explained changes in the concentration and pattern of PCB and PBDE congeners, as well as hepatic, plasma, and blubber vitamin A and E. Since vitamins and lipophilic contaminants accumulated in beluga whales in the same way in relation to most biological processes, including sex, reproduction, size, condition, and feeding ecology, it was important to control and reduce the number of these confounding factors before claiming any tissue vitamin change was indeed the result of chemical exposure. In doing so, it was found that vitamin A and E homeostasis was influenced by PCBs in beluga whales, resulting in reduced hepatic storage and increased plasma and blubber concentrations. Overall, these results suggest that liver, plasma, and inner blubber vitamin A and E concentrations can be sensitive biomarkers of contaminant exposure only if major confounding effects are taken into consideration. The implications of altered vitamin dynamics on the health of beluga whales is unknown at this time; however, as Arctic marine mammals face continued stress related to climate change, increased human disturbance and emergence of infectious diseases, this study can serve as essential baseline data that can be used to monitor the health status of western Arctic beluga whales. / Graduate / 0383 / 0329 / 0768 / jpdesforges@gmail.com

Devido à necessidade de se conhecer os impactos que as diversas atividades antropogênicas exercem sobre os ecossistemas torna-se relevante o estudo dos organismos aquáticos perante os resíduos tóxicos resultantes, com o objetivo de facilitar a identificação de áreas poluiídas ou contaminadas e estudos de meios atingidos por estes agentes poluentes. Estudo da microalga em contato com o fenol em concentrações conhecidas, compreende a determinação dos efeitos tóxicos e geração de metabólitos, caracterizando uma possível utilização deste microorganismo como bioindicador para contaminações do poluente. Determinou-se as concentrações de fenol capazes de em 24 horas inibirem o crescimento das células de L. polyedrum em 20 e 50% (IC 20 e IC 50) respectivamente 40 µmol.L-1 e 120 µmol.L-1. Identificou-se a necessidade de padronização das variáveis na execução dos ensaios dose-resposta com algas, permitindo construir protocolos que auxiliariam a obtenção de legislações que assegurem os limites de compostos tóxicos aos organismos costeiros. Calculou-se que a microalga L. polyedrum possui uma taxa de biodegradação do fenol por célula na média de aproximadamente (0,02 µmol.h-1.cel-1), capaz de biotransformar 120 µmol.L-1 de fenol em um período de 16 horas. Vias de biotransformação do fenol na microalga L.polyedrum se dão pela conjugação com a glutationa, catalisada por glutationa S-transferase e pela via metabólica de fenol hidroxilase e catecol 2,3-dihidroxigenase. Identificou-se a geração do ácido 2-hidroximucônico semialdeído, 1,2-dihidroxibenzeno (Catecol) e ácido 2-oxo 4-pentenóico como metabólitos resultantes da exposição de L. polyedrum ao fenol. O composto orgânico fenol é capaz de induzir um estado de aumento na atividade antioxidante da microalga L. polyedrum, sendo as enzimas superóxido dismutase e catalase os melhores biomarcadores, por terem sua expressão até três vezes maior no grupo exposto. Determinou-se que a razão GSH/GSSG no grupo tratado com fenol é menor, devido ao aumento de 20 ng.mL-1 de GSSG, expressando o efeito oxidativo no sistema glutationa, que em condições normais possui os níveis de GSSG muito abaixo dos de GSH. A avaliação fotossintética sugeriu que o fenol interferiu relativamente na fotossíntese da microalga em um curto intervalo de tempo, demonstrando a promissora sensibilidade a este poluente presente no ambiente marinho. / Due necessity of knowing and understand the impacts of diverse anthropogenic activities exerted above ecosystems became relevant the study of aquatic organisms exposed to toxic waste, this can facilitate the identification of polluted or contaminated areas. Study of microalgae in contact with phenol at known concentrations, comprehended a determination of the toxic effects and generation metabolites of characterizing the possible use of the organism as a bioindicator to contamination of the pollutant. In this work it was determined in 24 hours those inhibitor phenol concentrations of cell growth of L.polyedrum on 20% and 50% (IC 20 and IC 50) respectively 40 µmol.L-1 and 120 µmol.L-1. Acknowledged need for standardization of variables in the implementation of dose-response tests with algae, allowing you to build protocols that would help to obtain laws that ensure the limits of toxic compounds to coastal organisms. It was assumed that the L. polyedrum microalgae has a biodegradation rate of phenol per cell on average of about (0,02 µmol.h-1.cel-1), capable of biotransformation 120 µmol.L-1 of phenol in a period of 16 hours. Biotransformation pathways of phenol in the microalgae L. polyedrum occur by conjugation with glutathione, catalyzed by glutathione S-transferase and the metabolic pathway of phenol hydroxylase and catechol 2,3-dihydroxygenase. We identified 2- hydroxy muconic semialdehyde acid, 1,2-dihydroxybenzene (catechol) and 2-oxo-4-pentenoic acid as metabolites resulting from exposure to phenol. The phenol is able to induce a high active antioxidant enzymes on L. polyhedron, and the enzymes superoxide dismutase and catalase the best biomarkers since were induced three times more in the exposed group. It was determined that the GSH / GSSG ratio in the group treated with phenol, GSSG has an increase of 20 ng.mL-1. Evaluation suggested that the phenol interfered on photosynthesis of microalgae in a short time, showing promising sensitivity to this pollutant in the marine environment.

Devido à necessidade de se conhecer os impactos que as diversas atividades antropogênicas exercem sobre os ecossistemas torna-se relevante o estudo dos organismos aquáticos perante os resíduos tóxicos resultantes, com o objetivo de facilitar a identificação de áreas poluiídas ou contaminadas e estudos de meios atingidos por estes agentes poluentes. Estudo da microalga em contato com o fenol em concentrações conhecidas, compreende a determinação dos efeitos tóxicos e geração de metabólitos, caracterizando uma possível utilização deste microorganismo como bioindicador para contaminações do poluente. Determinou-se as concentrações de fenol capazes de em 24 horas inibirem o crescimento das células de L. polyedrum em 20 e 50% (IC 20 e IC 50) respectivamente 40 µmol.L-1 e 120 µmol.L-1. Identificou-se a necessidade de padronização das variáveis na execução dos ensaios dose-resposta com algas, permitindo construir protocolos que auxiliariam a obtenção de legislações que assegurem os limites de compostos tóxicos aos organismos costeiros. Calculou-se que a microalga L. polyedrum possui uma taxa de biodegradação do fenol por célula na média de aproximadamente (0,02 µmol.h-1.cel-1), capaz de biotransformar 120 µmol.L-1 de fenol em um período de 16 horas. Vias de biotransformação do fenol na microalga L.polyedrum se dão pela conjugação com a glutationa, catalisada por glutationa S-transferase e pela via metabólica de fenol hidroxilase e catecol 2,3-dihidroxigenase. Identificou-se a geração do ácido 2-hidroximucônico semialdeído, 1,2-dihidroxibenzeno (Catecol) e ácido 2-oxo 4-pentenóico como metabólitos resultantes da exposição de L. polyedrum ao fenol. O composto orgânico fenol é capaz de induzir um estado de aumento na atividade antioxidante da microalga L. polyedrum, sendo as enzimas superóxido dismutase e catalase os melhores biomarcadores, por terem sua expressão até três vezes maior no grupo exposto. Determinou-se que a razão GSH/GSSG no grupo tratado com fenol é menor, devido ao aumento de 20 ng.mL-1 de GSSG, expressando o efeito oxidativo no sistema glutationa, que em condições normais possui os níveis de GSSG muito abaixo dos de GSH. A avaliação fotossintética sugeriu que o fenol interferiu relativamente na fotossíntese da microalga em um curto intervalo de tempo, demonstrando a promissora sensibilidade a este poluente presente no ambiente marinho. / Due necessity of knowing and understand the impacts of diverse anthropogenic activities exerted above ecosystems became relevant the study of aquatic organisms exposed to toxic waste, this can facilitate the identification of polluted or contaminated areas. Study of microalgae in contact with phenol at known concentrations, comprehended a determination of the toxic effects and generation metabolites of characterizing the possible use of the organism as a bioindicator to contamination of the pollutant. In this work it was determined in 24 hours those inhibitor phenol concentrations of cell growth of L.polyedrum on 20% and 50% (IC 20 and IC 50) respectively 40 µmol.L-1 and 120 µmol.L-1. Acknowledged need for standardization of variables in the implementation of dose-response tests with algae, allowing you to build protocols that would help to obtain laws that ensure the limits of toxic compounds to coastal organisms. It was assumed that the L. polyedrum microalgae has a biodegradation rate of phenol per cell on average of about (0,02 µmol.h-1.cel-1), capable of biotransformation 120 µmol.L-1 of phenol in a period of 16 hours. Biotransformation pathways of phenol in the microalgae L. polyedrum occur by conjugation with glutathione, catalyzed by glutathione S-transferase and the metabolic pathway of phenol hydroxylase and catechol 2,3-dihydroxygenase. We identified 2- hydroxy muconic semialdehyde acid, 1,2-dihydroxybenzene (catechol) and 2-oxo-4-pentenoic acid as metabolites resulting from exposure to phenol. The phenol is able to induce a high active antioxidant enzymes on L. polyhedron, and the enzymes superoxide dismutase and catalase the best biomarkers since were induced three times more in the exposed group. It was determined that the GSH / GSSG ratio in the group treated with phenol, GSSG has an increase of 20 ng.mL-1. Evaluation suggested that the phenol interfered on photosynthesis of microalgae in a short time, showing promising sensitivity to this pollutant in the marine environment.