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The accumulation of polychlorinated biphenyls (PCBs) into humans was described using CoZMoMAN, a mechanistic multimedia fate and transport model coupled to a human food chain model. Model results demonstrated that concentration-age relationships for population cross-sections and individuals over time are not equivalent and that, under steady-state conditions, the lipid-normalized concentration of PCBs in an individual does not monotonically increase with age. By considering the decades-long emission history of PCBs in the model simulations, it was shown that an individual’s concentration mostly depends upon when she/he was born relative to the peak in emissions. Similarly, the two most influential factors controlling the shape of cross-sectional concentration-age trends obtained in human biomonitoring studies are the time lapse between the peak in emissions and sample collection and chemical elimination half-life. As a result, it should be possible to deduce information on these two factors from the shape of cross-sectional concentration-age trend. Reproductive behaviours (parity, age at birth, breastfeeding) were shown to potentially have a significant impact on exposure (and can contribute substantially to the observed variability in biomonitoring studies) though the mother’s reproductive history has a greater influence on the prenatal and postnatal exposures of her children than it does on her own cumulative lifetime exposure. A case study of the influence of dietary transitions in a hypothetical Arctic community demonstrated that dietary transitions are an important factor underlying the variability in PCB body burdens within and between subpopulations in addition to partially explaining the observed temporal trends. Comparison of PCB partitioning to various lipid materials suggested that 1) triolein is a good surrogate for human storage lipids; 2) liposomes are not an appropriate surrogate for human storage tissues; and 3) that partitioning into human MCF-7 cells is dominated by the storage lipids rather than by membrane lipids. Finally, a new bioenergetically-balanced bioaccumulation (3B) fish model is presented. Comparison of results from the 3B model with that of existing models revealed that feeding and growth rates used by previous fish bioaccumulation models were not bioenergetically consistent. Differences in biomagnification factors with fish size and temperature as a result of differing energetic requirements demonstrated the importance of the assumptions regarding growth rate and feeding rate.

Earlier studies on the relationship between mercury concentration in fish – or alternatively bioavailability of mercury in aquatic systems – and different abiotic oceanographic factors such as water temperature, pH and salinity, have shown that such associations often exist. The results are not always consistent between studies, however. The aim of this study is to investi­gate if this type of relationships can be established in Baltic herring, Clupea harengus, with the use of temporal monitoring data from the northern Bothnian Bay (northern Sweden), compiled within Swedish monitoring programmes. The abiotic factors being assessed in this study are water temperature, salinity, dissolved oxygen, pH and measurements of nutrient content in the water; phosphate, total phosphorus and total nitrogen. Relationships between these parameters and mercury concentration in herring were investi­gated using multiple linear regression. Generally however, relationships were absent, and only one significant association was found, a positive relationship between total phosphorus in water and herring mercury load. Difficulty to reveal relationships in the presence of confoun­ding factors, which cannot be controlled for when using monitoring data from the field, is suggested as one reason for the absence of such relationships. Furthermore, the somewhat incomplete monitoring data of abiotic factors likely made it hard to detect any relationships.

1,2-Dibromo-4-(1,2 dibromoethyl)cyclohexane or tetrabromoethylcyclohexane (TBECH) is an additive bromine based flame retardant used primarily in expandable polystyrene beads that are used mainly to produce thermal insulation for housing. Secondary uses include extrusion into polystyrene foam, adhesive in fabric and vinyl lamination, electrical cable coatings and construction materials. The technical formulation contains two diastereoisomers, α- and β-, which are present in equimolar amounts. Under elevated temperatures two other isomers, γ- and δ-, can be formed. The recent detection of TBECH in the environment and suggestions that all four isomers are androgenic prompted me to examine the bioaccumulation and biochemical effects of one of the isomers, β-, in a controlled laboratory environment. I purposely chose to examine this isomer as it has been detected in biota. Juvenile brown trout (Salmo trutta) were exposed to three different amounts of the β-isomer via their to three different amounts of the β-isomer via their food for 56 days (uptake phase). This was followed by a depuration phase in which all fish were exposed to unfortified food for 77 days. A fourth group of fish were exposed to unfortified food for the duration of the experiment. On days 0, 7, 14, 35, 49, 56, 63, 77, 91, 105, and 133 eight fish from each treatment group were sacrificed and liver, plasma, thyroid and gonad gland were collected and whole-fish (carcass minus tissues above) were collected. Residues of β-isomer were analyzed in the whole-fish and in liver extracts by gas chromatography mass spectrometry in the electron ionization while estradiol (E2), 11-ketotestosterone (11-KT) and testosterone (T) were extracted from plasma and analysed by liquid chromatography tandem mass spectrometry. The bioaccumulation of β-isomer was similar in fish from all treatment groups with steady-state occurring before the end of the uptake phase. Depuration of the β-isomer from fish obeyed first order kinetics and there were no statistically significant differences in the depuration half life (t1/2) among the treatment groups: 22.5 ± 10.4 (low), 13.5 ± 5.9 (med) and 13.8 ± 2.2 (high) days. Steady-state biomagnification factors were much smaller than 1 for fish in all treatment groups. I was unable to detect debrominated metabolites in liver or whole-fish extracts and I also found no evidence of isomerization of the β-isomer to other isoforms in vivo. While there were some differences in E2, T and 11-KT levels in plasma of fish from the treated groups relative to plasma in fish from the control group there were no clear, consistent, discerning trends.

The major objectives of this research were to examine the bioaccumulation parameters [depuration rates (kd), half life (t1/2) and biomagnification factor (BMF)] of individual isomers of hexabromocyclododecane (HBCD, C12H18Br6) in fish and to test the hypothesis of in vivo bioisomerization. This was done by exposing three groups of juvenile rainbow trout (Oncorhynchus Mykiss) to food fortified with known concentrations of an individual diastereoisomer (α, β, γ) for 56 days (uptake phase) followed by 112 days (depuration phase) of unfortified food. A fourth group of fish were exposed to unfortified food for the duration of the experiment. Fish (n=4) from all four aquaria were sacrificed on days 0, 7, 14, 56, 63, 70, 112 and 168 and muscle tissue was extracted and analyzed for diastereoisomer concentrations by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS). Bioaccumulation of the γ diastereoisomer was linear during the uptake phase while the α and β diastereoisomers were found to increase exponentially with respective doubling times of 14.1 and 20.5 days. Both the β and γ diastereoisomers followed first order depuration kinetics with calculated t1/2’s of 94 ± 25 and 84 ± 51 (± 1 × standard error) days, respectively. The BMF for the α diastereoisomer (BMF = 4.1) was one and a half times greater than the β-diastereoisomer (BMF = 2.6) and about one fifth larger than the γ-diastereoisomer (BMF = 3.6). The large BMF for the α diastereoisomer is consistent with this diastereoisomer dominating higher trophic level organisms in wildlife. Although the BMF of the β diastereoisomer suggests that it will biomagnify, because it is present in small quantities in commercial mixtures it is rarely detected in environmental samples. Results from these studies also provide evidence of bioisomerization of the β and γ diastereoisomers. Most importantly, the α diastereoisomer which was recalcitrant to bioisomerization by juvenile rainbow trout in this study and known to be the dominant diastereosiomer in fish, was bioformed from both the β and γ diastereoisomers. To our knowledge, this is the first report of bioisomerization of a halogenated organic pollutant in biota.

1,2-Dibromo-4-(1,2 dibromoethyl)cyclohexane or tetrabromoethylcyclohexane (TBECH) is an additive bromine based flame retardant used primarily in expandable polystyrene beads that are used mainly to produce thermal insulation for housing. Secondary uses include extrusion into polystyrene foam, adhesive in fabric and vinyl lamination, electrical cable coatings and construction materials. The technical formulation contains two diastereoisomers, α- and β-, which are present in equimolar amounts. Under elevated temperatures two other isomers, γ- and δ-, can be formed. The recent detection of TBECH in the environment and suggestions that all four isomers are androgenic prompted me to examine the bioaccumulation and biochemical effects of one of the isomers, β-, in a controlled laboratory environment. I purposely chose to examine this isomer as it has been detected in biota. Juvenile brown trout (Salmo trutta) were exposed to three different amounts of the β-isomer via their to three different amounts of the β-isomer via their food for 56 days (uptake phase). This was followed by a depuration phase in which all fish were exposed to unfortified food for 77 days. A fourth group of fish were exposed to unfortified food for the duration of the experiment. On days 0, 7, 14, 35, 49, 56, 63, 77, 91, 105, and 133 eight fish from each treatment group were sacrificed and liver, plasma, thyroid and gonad gland were collected and whole-fish (carcass minus tissues above) were collected. Residues of β-isomer were analyzed in the whole-fish and in liver extracts by gas chromatography mass spectrometry in the electron ionization while estradiol (E2), 11-ketotestosterone (11-KT) and testosterone (T) were extracted from plasma and analysed by liquid chromatography tandem mass spectrometry. The bioaccumulation of β-isomer was similar in fish from all treatment groups with steady-state occurring before the end of the uptake phase. Depuration of the β-isomer from fish obeyed first order kinetics and there were no statistically significant differences in the depuration half life (t1/2) among the treatment groups: 22.5 ± 10.4 (low), 13.5 ± 5.9 (med) and 13.8 ± 2.2 (high) days. Steady-state biomagnification factors were much smaller than 1 for fish in all treatment groups. I was unable to detect debrominated metabolites in liver or whole-fish extracts and I also found no evidence of isomerization of the β-isomer to other isoforms in vivo. While there were some differences in E2, T and 11-KT levels in plasma of fish from the treated groups relative to plasma in fish from the control group there were no clear, consistent, discerning trends.

The accumulation of polychlorinated biphenyls (PCBs) into humans was described using CoZMoMAN, a mechanistic multimedia fate and transport model coupled to a human food chain model. Model results demonstrated that concentration-age relationships for population cross-sections and individuals over time are not equivalent and that, under steady-state conditions, the lipid-normalized concentration of PCBs in an individual does not monotonically increase with age. By considering the decades-long emission history of PCBs in the model simulations, it was shown that an individual’s concentration mostly depends upon when she/he was born relative to the peak in emissions. Similarly, the two most influential factors controlling the shape of cross-sectional concentration-age trends obtained in human biomonitoring studies are the time lapse between the peak in emissions and sample collection and chemical elimination half-life. As a result, it should be possible to deduce information on these two factors from the shape of cross-sectional concentration-age trend. Reproductive behaviours (parity, age at birth, breastfeeding) were shown to potentially have a significant impact on exposure (and can contribute substantially to the observed variability in biomonitoring studies) though the mother’s reproductive history has a greater influence on the prenatal and postnatal exposures of her children than it does on her own cumulative lifetime exposure. A case study of the influence of dietary transitions in a hypothetical Arctic community demonstrated that dietary transitions are an important factor underlying the variability in PCB body burdens within and between subpopulations in addition to partially explaining the observed temporal trends. Comparison of PCB partitioning to various lipid materials suggested that 1) triolein is a good surrogate for human storage lipids; 2) liposomes are not an appropriate surrogate for human storage tissues; and 3) that partitioning into human MCF-7 cells is dominated by the storage lipids rather than by membrane lipids. Finally, a new bioenergetically-balanced bioaccumulation (3B) fish model is presented. Comparison of results from the 3B model with that of existing models revealed that feeding and growth rates used by previous fish bioaccumulation models were not bioenergetically consistent. Differences in biomagnification factors with fish size and temperature as a result of differing energetic requirements demonstrated the importance of the assumptions regarding growth rate and feeding rate.

The major objectives of this research were to examine the bioaccumulation parameters [depuration rates (kd), half life (t1/2) and biomagnification factor (BMF)] of individual isomers of hexabromocyclododecane (HBCD, C12H18Br6) in fish and to test the hypothesis of in vivo bioisomerization. This was done by exposing three groups of juvenile rainbow trout (Oncorhynchus Mykiss) to food fortified with known concentrations of an individual diastereoisomer (α, β, γ) for 56 days (uptake phase) followed by 112 days (depuration phase) of unfortified food. A fourth group of fish were exposed to unfortified food for the duration of the experiment. Fish (n=4) from all four aquaria were sacrificed on days 0, 7, 14, 56, 63, 70, 112 and 168 and muscle tissue was extracted and analyzed for diastereoisomer concentrations by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS). Bioaccumulation of the γ diastereoisomer was linear during the uptake phase while the α and β diastereoisomers were found to increase exponentially with respective doubling times of 14.1 and 20.5 days. Both the β and γ diastereoisomers followed first order depuration kinetics with calculated t1/2’s of 94 ± 25 and 84 ± 51 (± 1 × standard error) days, respectively. The BMF for the α diastereoisomer (BMF = 4.1) was one and a half times greater than the β-diastereoisomer (BMF = 2.6) and about one fifth larger than the γ-diastereoisomer (BMF = 3.6). The large BMF for the α diastereoisomer is consistent with this diastereoisomer dominating higher trophic level organisms in wildlife. Although the BMF of the β diastereoisomer suggests that it will biomagnify, because it is present in small quantities in commercial mixtures it is rarely detected in environmental samples. Results from these studies also provide evidence of bioisomerization of the β and γ diastereoisomers. Most importantly, the α diastereoisomer which was recalcitrant to bioisomerization by juvenile rainbow trout in this study and known to be the dominant diastereosiomer in fish, was bioformed from both the β and γ diastereoisomers. To our knowledge, this is the first report of bioisomerization of a halogenated organic pollutant in biota.

Inúmeros pesticidas são usados na agricultura, para controle de pragas e ervas daninhas. Dentre eles destaca-se o herbicida atrazina, intensivamente utilizado nas culturas de cana-de-açúcar, milho e sorgo, que ocupam extensas áreas no estado de São Paulo. Grande parcela do herbicida, que é aplicado na agricultura, entra em contato com o solo, podendo ser lixiviado, atingindo as águas superficiais. Neste sentido, alguns animais como, por exemplo, moluscos bivalves, podem ser utilizados como monitores biológicos do ambiente aquático e auxiliar no estudo da ecotoxicologia. Considerando o risco de contaminação do ambiente aquático pela atrazina, propõe-se, no presente trabalho, desenvolver uma metodologia de análise daquele herbicida nos tecidos nas espécies de bivalves límnicos Anodontites trapesialis (LAMARCK, 1819) e Corbicula fluminea (Muller, 1789), validar esse método e, finalmente, verificar se ocorre a bioacumulação do herbicida nas partes moles dessas duas espécies. Como técnica de extração utilizou-se a extração líquido- líquido e como técnica de análise, a cromatografia líquida de alta eficiência (CLAE). / Large amount of pesticides have been used for the control of agriculture pests and weeds. Particularly important among herbicides is atrazine, extensively employed in cultures of sugar cane, corn and sorghum, that occupies an extensive area in São Paulo state. Large portions of atrazine, applied in the agricultural fields, leaches from the soil to surface water systems. In this way, some organisms such as fresh- water mollusks bivalves, can be used as biological monitors of aquatic environments, contributing for ecotoxicology studies. Considering the existence of risk of contamination by atrazine of the aquatic environment, the purpose of this work was, (i) to develop a method for the analysis of atrazine in the fresh- water bivalves species Anodontites trapesialis (LAMARCK, 1819) and Corbicula fluminea (MULLER, 1789), (ii) to validate such method and, (iii) to detect if these organisms can bioaccumulate atrazine in their tissues. This method involved a simple liquid-liquid extraction procedure, followed by high- performance liquid chromatographic analysis (HPLC).

M.Sc. (Zoology) / Axenic cultures of Euglena gracilis in different basal medium concentrations, to simulate eutrophic conditions, were exposed to different concentrations of Monocrotophos and Dichlorvos to determine the effect of the pesticides on the growth reaction. The effect of the pesticides on the chlorophyll a content of test organisms exposed to equivalent toxicities of pesticides was determined. The amount of pesticide accumulated and me tabolised was determined by the choline esterase method and by gaschromatography. More pesticide was found to be accumulated and metabolised by organisms in the lower concentration of basal medium.