Brominated flame retardants (BFR) such as hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), bis(2-ethylhexyl)tetrabromophthalate (BEHTBP), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE) are contaminants of environmental concern. These BFRs are replacement alternatives for some of the major production BFRs, which have been restricted from the marketplace due to their adverse health effects. Their presence in environmental matrices, including wild birds, suggests they should be tested for possible toxic effects. BFR alternatives have been detected in the eggs of colonial fish-eating birds, suggesting maternal transfer during ovogenesis and the potential for these chemicals to bioaccumulate through the food chain. However, information regarding the toxicity of HCDBCO, BEHTBP, BTBPE and DBDPE exposure in birds is lacking. This thesis consisted of a combined in vitro/in ovo approach to determine: 1) the concentration-dependent effects of these four BFR alternatives in chicken embryonic hepatocytes (CEH), and 2) the dose-dependent effects of HCDBCO and BTBPE in chicken embryos following injection into the air cell of eggs prior to incubation. Changes in the mRNA expression levels of genes previously found to be responsive to other BFRs were assessed in CEH and liver tissue, in addition to examining overt toxicity (i.e. cytotoxicity, pipping success). None of the BFRs tested were cytotoxic up to 60 µM HCDBCO, 60 µM BEHTBP, 1.4 µM BTBPE or 0.2 µM DBDPE in CEH. Injection doses up to 50 µg/g egg HCDBCO and 10 µg/g egg BTBPE had no effect on embryonic pipping success. The accumulation of HCDBCO and BTBPE was variable in liver and did not follow a linear uptake pattern with respect to injection dose, due in part to difficulties with the solubility of these chemicals in the dimethyl sulfoxide (DMSO) vehicle. In, CEH, HCDBCO caused a decrease in CYP1A4/5 mRNA at all concentrations tested, while CYP2H1 and CYP3A37 were induced only at 10 µM. In contrast, only TTR mRNA was down-regulated in hepatic tissue at all injection concentrations of HCDBCO. The highest concentration of BTBPE induced CYP1A4/5 mRNA to 115- and 18-fold in CEH, and 6.5- and 1.8-fold in liver tissue. In vitro and in ovo exposure to BTBPE caused a concentration-dependent decrease in DIO3 mRNA, while CYP3A37 was down-regulated 2-fold at 10 µg/g in liver tissue. In CEH, DBDPE induced CYP1A4/5 mRNA to a maximum of 29- and 59-fold at 0.2 µM, and increases in DIO1 mRNA and decreases in CYP3A37 mRNA were also observed. None of the gene targets were responsive to BEHTBP exposure in CEH. This is the first study to report on the toxicological and molecular effects of HCDBCO, BEHTBP, BTBPE and DBDPE in an avian species. Using this combined in vitro/in ovo approach has permitted the characterization of these four BFR alternatives by defining possible mechanisms of biological action in a model avian species, the chicken.

Chickpea production in the short growing season of the Canadian Prairies is still a challenging task due to excessive and continuous vegetative growth which often results in severe yield and quality reduction. This study examined the effects of three plant growth retardants (PGR), Chlormequat Chloride (CCC), Prohexadione Calcium and Trinexapac Ethyl applied during flowering stage on vegetative growth, seed quality, yield and crop maturity of the Kabuli chickpea cultivar CDC Frontier. Field experiments were conducted at Brooks and Bow Island in southern Alberta in the 2010 and 2011 growing seasons. Four concentrations of each PGR were applied at 10, 20 and 30 days after flowering (DAF) stages. During the 2010 growing season the crop experienced above average moist and cooler temperature conditions. In contrast, later half of the 2011 growing season was above average dry and hot. None of the three PGR tested in this study had a significant effect on plant height at 30 days after treatments or on above ground biomass plant-1 at harvest. Application of PGR had no significant effects on the number of seeds m-2, except at the Brooks rain-fed site in 2011 where the PGR treatment applied at 10 and 20 DAF increased the number of seeds m-2 at harvest. An increase of 1000-seed weight of marketable seeds was obtained with Prohexadione Calcium and Trinexapac Ethyl applications at Bow Island, but the effects were not consistent across sites and years. Results suggested that the effect of PGR on 1000-seed weight of marketable seeds mainly depended upon the growing environment and the type of PGR. In general, PGR applications reduced the total and marketable seed yields. Application of Prohexadione Calcium and Trinexapac Ethyl at the Bow Island site delayed crop maturity in 2011. In contrast, the application of CCC at 6000 mg L-1 at 20 DAF accelerated crop maturity at the Brooks irrigated site in 2011. In addition to this main study, the potential effects of Pyraclostrobin and Prothioconazole fungicides on the activities of the three PGR were compared by a separate experiment conducted at the Brooks irrigated site in 2011. The results of that study revealed that there were no significant differences in the effects of PGR on chickpea vegetative growth, seed yield parameters and maturity when they were applied as a mixture with either Pyraclostrobin or Prothioconazole fungicide. In summary, results revealed that PGR applied during flowering stage were not effective on controlling vegetative growth of chickpea and did not improve seed yield and crop maturity. Their effects on yield-related traits were highly inconsistent. Thus, it can be concluded that the application of PGR is not a reliable agronomic option to handle the production issues associated with continues vegetative growth at the late reproductive stage of the chickpea cultivar CDC Frontier under the western Canadian growing conditions.

Retail stores are an environment with a rich diversity of toxic chemicals typically found in consumer products. Among these chemicals, semi-volatile organic compounds (SVOCs) are an important class with great health concerns. Phthalates and polybrominated diphenyl ethers (PBDEs) are high production volume SVOC chemicals pervasively used in plastics and other consumer products. Exposure to them may cause serious adverse health effects, including endocrine disruption. They, however, have not been widely studied in retail environments. In this study, indoor air samples were collected from 15 retail stores in Austin, TX and University Park, PA. Some of these stores were revisited on different temperate seasons to account for weather variability. Indoor concentrations of the most ubiquitous pollutants were correlated with several building characteristics, including retailer type, temperature, and building use characteristics. Collected data shows a wider variety of phthalates and PBDEs, as well as higher indoor airborne concentrations for large department stores as compared to grocery stores, which typically have fewer sources in comparison. / text

Tradtional brominated flame retardants (BFRs), namely the polybrominated diphenyl ethers (PBDEs), have persistent, bioaccumulative, and toxic properties that have resulted in the phase out of their production and their be banned in certain jurisdictions. To meet regulatory flame retardancy requirements, non-PBDE BFRs have entered the marketplace. Much remains unknown regarding the environmental fate and toxicity of these emerging BFRs. The objective of this thesis was to use outdoor mesocosms to examine the fate and toxicity of three emerging BFRs; bis(tribromophenoxy)ethane (BTBPE), tetrabromobisphenol A bis(dibromopropyl ether) (TBBPA-DBPE), and BZ-54, which consists of two BFRs, ethylhexyl-tetrabromobenzoate (EHTeBB) and bis(ethylhexyl)tetrabromophthalate (BEHTBP). While it was difficult to accurately determine degradation rates because of fluctuating concentrations, the estimated half-lives indicated these compounds are persistent (> 60 days in sediments). The partitioning of the compounds between the particulates and the sediment resulted in differential degradation rates (greater in the particulates), and products formed; those formed on the particulates were consistent with photodegradation products. The effects of these emerging BFRs on Hyalella azteca and the benthic macroinvertebrate community were assessed through the use of in situ exposure and sampling techniques. The in situ Hyalella cages showed a high degree of variability for most endpoints, regardless of their placement (e.g., water column vs. sediment) in the mesocosm. BTBPE accumulated in the H. azteca (0.03 – 1.4 ng/g ww), however this was not associated with any changes in growth or reproduction. There was high variability in abundance and diversity between the mesocosms, which limited the ability to detect statistically significant differences. Interestingly, the BZ-54 treated mesocosms had the greatest abundance, and the least amount of community diversity. This thesis examined the bioaccumulation potential of these compounds in fathead minnow (Pimephales promelas), as well as the associated effects on growth and development as measured through physical and biochemical endpoints. There was considerable uptake and persistence of BTBPE and TBBPA-DBPE, as well as indication of metabolism of these compounds, but limited physical effects observed. There were indications of increased oxidative stress in the BZ-54 treatment, and increased induction of vitellogenin in fathead minnow from the BTBPE treatment. / Environment Canada's Chemicals Management Plan

Computational Fluid Dynamics (CFD) codes are being increasingly used in the field of fire safety engineering. They provide, amongst other things, velocity, species and heat flux distributions throughout the computational domain. The various sub-models associated with these have been developed sufficiently to reduce the errors below 10%-15%, and work continues on reducing these errors yet further. However, the uncertainties introduced by using material properties as an input for these models are considerably larger than those from the other sub-models, yet little work is being done to improve these. Most of the data for these material properties comes from traditional (standard) tests. It is known that these properties are not intrinsic, but are test-specific. Thus, it can be expected that the errors incurred when using these in computations can be significant. Research has been held back by a lack of understanding of the basic factors that determine material flammability. The term “flammability” is currently used to encompass a number of definitions and “properties” that are linked to standardised test methodologies. In almost all cases, the quantitative manifestations of “flammability” are a combination of material properties and environmental conditions associated with the particular test method from which they were derived but are not always representative of parameters linked intrinsically with the tested material. The result is that even the best-defined parameters associated with flammability cannot be successfully introduced into fire models to predict ignition or fire growth. The aim of this work is to develop a new approach to the interpretation of standard flammability tests in order to derive the (intrinsic) material properties; specifically, those properties controlling ignition. This approach combines solid phase and gas modelling together with standard tests using computational fluid dynamics (CFD), mass fraction of flammable gases and lean flammability limits (LFL). The back boundary condition is also better defined by introducing a heat sink with a high thermal conductivity and a temperature dependant convective heat transfer coefficient. The intrinsic material properties can then be used to rank materials based on their susceptibility to ignition and, furthermore, can be used as input data for fire models. Experiments in a standard test apparatus (FPA) were performed and the resulting data fitted to a complex pyrolysis model to estimate the (intrinsic) material properties. With these properties, it should be possible to model the heating process, pyrolysis, ignition and related material behaviour for any adequately defined heating scenario. This was achieved, within bounds, during validation of the approach in the Cone Calorimeter and under ramped heating conditions in the Fire Propagation Apparatus (FPA). This work demonstrates that standard flammability and material tests have been proven inadequate for the purpose of obtaining the “intrinsic” material properties required for pyrolysis models. A significant step has been made towards the development of a technique to obtain these material properties using test apparatuses, and to predict ignition of the tested materials under any heating scenario. This work has successfully demonstrated the ability to predict the driving force (in-depth temperature distribution) in the ignition process. The results obtained are very promising and serve to demonstrate the feasibility of the methodology. The essential outcomes are the “lessons learnt”, which themselves are of great importance to the understanding and further development of this technique. One of these lessons is that complex modelling in conjunction with current standard flammability test cannot currently provide all required parameters. The uncertainty of the results is significantly reduced when using independently determined parameters in the model. The intrinsic values of the material properties depend significantly on the accuracy of the model and precision of the data.

Tetrabromobisphenol A, (TBBPA or Br4BPA), is a widely used brominated flame retardant (BFR). Although TBBPA and its breakdown products been found in river sediments, the environmental impact of their contamination is largely unknown. One breakdown product of TBBPA is bisphenol A (BPA), which has been studied intensively for its toxicology because it is used in the manufacturing of plastics and leaches from food containers, water bottles and pipes. Other breakdown products of TBBPA include tribromobisphenol A (Br3BPA), dibromobisphenol A (Br2BPA), and monobromobisphenol A (BrBPA) but little is known about their toxicology. Since TBBPA is toxic, there is a need to search for an alternative BFR, with one being tetrabromobisphenol A bis(2,3-dibromopropylether) or TBBPA-DBPE. However, almost nothing is known about the toxicology of this compound. Hence, two rainbow trout cell lines, RTL-W1 from liver and RTgill-W1 from gill, were used to evaluate the cellular toxicity of TBBPA, BPA, BrBPA, Br2BPA, Br3BPA and TBBPA-DBPE. The cells were exposed to these compounds for 24 h in the basal medium, L-15, to study their cytotoxicity and in L-15 with fetal bovine serum (FBS) to evaluate their capacity to induce 7-ethoxyresorufin o-deethylase (EROD) activity. Viability was measured with three fluorometric indicator dyes: Alamar Blue (AB) for metabolism, 5-carboxyfluorescein diacetate acetoxymethyl (CFDA AM) for cell membrane integrity, and Neutral Red (NR) for lysosomal activity. The concentrations causing a 50 % reduction in viability (EC50) as measured with these three dyes were used to compare the relative cytotoxicity of these chemicals. For both cell lines and with all viability endpoints, TBBPA was the most cytotoxic, with EC50s ranging from 2.33 to 3.11 ug/ml. BPA, BrBPA, Br2BPA, and Br3BPA also caused dose-dependent declines in cell viability but showed no consistent order of potency. None of the six compounds induced EROD activity, which suggests that they do not activate the aryl hydrocarbon receptor (AhR). Regardless of the endpoint or cell line, TBBPA-DBPE was not cytotoxic. This suggests that, from a toxicological perspective, this compound may be a suitable replacement for TBBPA as a BFR. BPA stood out from the other compounds in two regards. BPA caused a dose-dependent decline in cell viability for cultures in L-15 with FBS, whereas for the other compounds, little or no change in viability was seen in cultures with FBS. BPA elicited a decline in the ability of cells to reduce AB almost immediately upon its addition to cultures in a simple buffer, whereas as for other compounds a decline took time to develop. These results suggest that BPA exerts its cytotoxicity by a different mechanism different from the other compounds.

Brominated flame retardants (BFR) such as hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), bis(2-ethylhexyl)tetrabromophthalate (BEHTBP), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE) are contaminants of environmental concern. These BFRs are replacement alternatives for some of the major production BFRs, which have been restricted from the marketplace due to their adverse health effects. Their presence in environmental matrices, including wild birds, suggests they should be tested for possible toxic effects. BFR alternatives have been detected in the eggs of colonial fish-eating birds, suggesting maternal transfer during ovogenesis and the potential for these chemicals to bioaccumulate through the food chain. However, information regarding the toxicity of HCDBCO, BEHTBP, BTBPE and DBDPE exposure in birds is lacking. This thesis consisted of a combined in vitro/in ovo approach to determine: 1) the concentration-dependent effects of these four BFR alternatives in chicken embryonic hepatocytes (CEH), and 2) the dose-dependent effects of HCDBCO and BTBPE in chicken embryos following injection into the air cell of eggs prior to incubation. Changes in the mRNA expression levels of genes previously found to be responsive to other BFRs were assessed in CEH and liver tissue, in addition to examining overt toxicity (i.e. cytotoxicity, pipping success). None of the BFRs tested were cytotoxic up to 60 µM HCDBCO, 60 µM BEHTBP, 1.4 µM BTBPE or 0.2 µM DBDPE in CEH. Injection doses up to 50 µg/g egg HCDBCO and 10 µg/g egg BTBPE had no effect on embryonic pipping success. The accumulation of HCDBCO and BTBPE was variable in liver and did not follow a linear uptake pattern with respect to injection dose, due in part to difficulties with the solubility of these chemicals in the dimethyl sulfoxide (DMSO) vehicle. In, CEH, HCDBCO caused a decrease in CYP1A4/5 mRNA at all concentrations tested, while CYP2H1 and CYP3A37 were induced only at 10 µM. In contrast, only TTR mRNA was down-regulated in hepatic tissue at all injection concentrations of HCDBCO. The highest concentration of BTBPE induced CYP1A4/5 mRNA to 115- and 18-fold in CEH, and 6.5- and 1.8-fold in liver tissue. In vitro and in ovo exposure to BTBPE caused a concentration-dependent decrease in DIO3 mRNA, while CYP3A37 was down-regulated 2-fold at 10 µg/g in liver tissue. In CEH, DBDPE induced CYP1A4/5 mRNA to a maximum of 29- and 59-fold at 0.2 µM, and increases in DIO1 mRNA and decreases in CYP3A37 mRNA were also observed. None of the gene targets were responsive to BEHTBP exposure in CEH. This is the first study to report on the toxicological and molecular effects of HCDBCO, BEHTBP, BTBPE and DBDPE in an avian species. Using this combined in vitro/in ovo approach has permitted the characterization of these four BFR alternatives by defining possible mechanisms of biological action in a model avian species, the chicken.

Orientador : Elizabeth Orika Ono / Banca: João Domingos Rodrigues / Banca: Vandeir Francisco Guimarães / Banca: Manoel Abilio de Queiroz / Banca: Silvio José Bicudo / Resumo: Tratamentos com reguladores vegetais foram estudados em plantas de soja (Glycine max (L.) Merrill cv. BRS-184) para avaliar o teor de clorofila das folhas, a altura da planta, o número de ramificações e altura de vagens. O experimento foi conduzido em casa de vegetação do Departamento de Botânica do Instituto de Biociências de Botucatu - UNESP. O delineamento experimental utilizado foi inteiramente casualizado, com três repetições e oito tratamentos (testemunha; GA3 100 mg L-1; BAP 100 mg L-1; IBA 100 mg L-1; Stimulate® (IBA+GA3+Cinetina) 20 mL L-1; cloreto de mepiquat 100 mg L-1; cloreto de mepiquat 100 mg L-1+BAP 100 mg L-1+IBA 100 mg L-1 e ethephon 600 mg L-1. Os tratamentos foram aplicados três vezes, espaçados em 30 dias durante o ciclo da planta a partir do 43º dia e foram realizadas seis avaliações espaçados em 13 dias. Os tratamentos com BAP, ethephon e cloreto de mepiquat + IBA + BAP mantiveram o teor de clorofila nas folhas alto até o final do ciclo da planta. A altura de plantas foi menor que a testemunha em todos os tratamentos a partir de 90 dias após a semeadura, com exceção do tratamento com GA3, que manteve a altura de plantas superior durante todo ciclo da cultura. As ramificações das plantas foram incrementadas pelo tratamento com ethephon, que apresentou, a altura da primeira vagem inferior à testemunha. No tratamento com GA3, a altura da primeira vagem foi superior. / Abstract: Treatments with plant growth regulators were studied in soybean plants (Glycine max (L.) Merrill cv. BRS-184) to assess the leaf chlorophyll content, the ramification number and the height of the pods. The experiment has been carried out at the greenhouse of the Botanic Department, Bioscience Institute, University of the Sao Paulo State - UNESP, campus of Rubiao Junior, Botucatu, Brazil. The used experimental design delineation was completely randomized block with three replications and eight treatments (control; GA3 100 mg L-1; BAP 100 mg L-1; IBA 100 mg L-1; Stimulate® (IBA+GA3+Cinetin) 20 mL L-1; mepiquat chloride 100 mg L-1; mepiquat chloride 100 mg L-1+BAP 100 mg L-1+IBA 100 mg L-1 and ethephon 600 mg L-1. The treatments were applied three times every 30 days during the plant cycle after 43 days and six evaluations have been made every 13 days. The treatments with BAP, ethephon and mepiquat chloride + IBA + BAP maintained the high chlorophyll content until the end of the plant cycle. The height of the plants was lower than the control in all treatments after the 90th day of sowing, excepting the treatment with GA3, which maintained the height of the plants during the cycle of cultivation. The plant stems were increased by the ethephon treatment; however, the height of the first pod was the lowest in this treatment and the highest in the treatment with GA3. / Doutor

Brominated flame retardants (BFR) such as hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), bis(2-ethylhexyl)tetrabromophthalate (BEHTBP), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE) are contaminants of environmental concern. These BFRs are replacement alternatives for some of the major production BFRs, which have been restricted from the marketplace due to their adverse health effects. Their presence in environmental matrices, including wild birds, suggests they should be tested for possible toxic effects. BFR alternatives have been detected in the eggs of colonial fish-eating birds, suggesting maternal transfer during ovogenesis and the potential for these chemicals to bioaccumulate through the food chain. However, information regarding the toxicity of HCDBCO, BEHTBP, BTBPE and DBDPE exposure in birds is lacking. This thesis consisted of a combined in vitro/in ovo approach to determine: 1) the concentration-dependent effects of these four BFR alternatives in chicken embryonic hepatocytes (CEH), and 2) the dose-dependent effects of HCDBCO and BTBPE in chicken embryos following injection into the air cell of eggs prior to incubation. Changes in the mRNA expression levels of genes previously found to be responsive to other BFRs were assessed in CEH and liver tissue, in addition to examining overt toxicity (i.e. cytotoxicity, pipping success). None of the BFRs tested were cytotoxic up to 60 µM HCDBCO, 60 µM BEHTBP, 1.4 µM BTBPE or 0.2 µM DBDPE in CEH. Injection doses up to 50 µg/g egg HCDBCO and 10 µg/g egg BTBPE had no effect on embryonic pipping success. The accumulation of HCDBCO and BTBPE was variable in liver and did not follow a linear uptake pattern with respect to injection dose, due in part to difficulties with the solubility of these chemicals in the dimethyl sulfoxide (DMSO) vehicle. In, CEH, HCDBCO caused a decrease in CYP1A4/5 mRNA at all concentrations tested, while CYP2H1 and CYP3A37 were induced only at 10 µM. In contrast, only TTR mRNA was down-regulated in hepatic tissue at all injection concentrations of HCDBCO. The highest concentration of BTBPE induced CYP1A4/5 mRNA to 115- and 18-fold in CEH, and 6.5- and 1.8-fold in liver tissue. In vitro and in ovo exposure to BTBPE caused a concentration-dependent decrease in DIO3 mRNA, while CYP3A37 was down-regulated 2-fold at 10 µg/g in liver tissue. In CEH, DBDPE induced CYP1A4/5 mRNA to a maximum of 29- and 59-fold at 0.2 µM, and increases in DIO1 mRNA and decreases in CYP3A37 mRNA were also observed. None of the gene targets were responsive to BEHTBP exposure in CEH. This is the first study to report on the toxicological and molecular effects of HCDBCO, BEHTBP, BTBPE and DBDPE in an avian species. Using this combined in vitro/in ovo approach has permitted the characterization of these four BFR alternatives by defining possible mechanisms of biological action in a model avian species, the chicken.

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