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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.

Use of fish cell lines to compare the cytotoxicity of Tetrabromobisphenol A with its degradation products and with an alternative brominated flame retardant

Wong, Janice 06 November 2014 (has links)
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.

Effects of Developmental Exposures of Two Emerging Environmental Toxicants on Estrogen-Sensitive Endpoints

Hill, Corinne E 17 July 2015 (has links)
Thousands of synthetic chemicals have been released into the environment, causing widespread exposures of wildlife and humans alike. Some of these chemicals are known to disrupt aspects of hormone action thus inducing abnormalities in endocrine tissues and organs. Bisphenol S (BPS) and tetrabromobisphenol A (TBBPA), two largely unstudied chemicals commonly used in consumer products, are suspected to have endocrine disrupting properties based on their similar chemical structures to known endocrine disrupting chemicals (EDCs). To determine whether developmental exposure to BPS or TBBPA induced abnormalities in the ovary, mice were administered oil, BPS or TBBPA during pregnancy and lactation. The ovaries of female offspring were examined for gross morphological, immunohistological and gene expression differences at postnatal day (PND) 22 and week 16. To determine whether these exposures alter responses to hormones, two females from each litter were administered either oil or ethinyl estradiol (EE2) from PND 19-21. Our study identified significant differences in ovarian follicular formation and gene expression after developmental TBBPA and BPS exposures. Most effects were observed at PND22 (pre-puberty), and were apparent after the EE2 challenge, suggesting that changes induced by BPS and TBBPA are age- and hormone- dependent. Our results are consistent with the hypothesis that TBBPA and BPS are EDCs; that these compounds can disrupt development of the ovary; and that the observed effects of TBBPA and BPS exposure are similar to risk factors for ovarian diseases including cancer. These findings may indicate that widespread exposures to BPS and TBBPA could have implications for public health.

Fate Mechanisms and Removal of Tetrabromobisphenol-A (2,2’,6,6’-Tetrabromo-4,4’-isopropylidenediphenol) in the Activated Sludge Process

Potvin, Christopher Michael 10 May 2012 (has links)
A novel method for determination of tetrabromobisphenol-A (TBBPA), was developed using gas chromatography-negative ion chemical ionization-mass spectrom- etry (GC-NCI-MS). Samples of municipal wastewater treatment plant (WWTP) influent were analyzed for TBBPA. Levels ranged from 1 to 41 ng/L, with an average of 20 ± 14 ng/L. Matrix effects were shown to be 30 ± 17 % in the influent and -30 ± 11 % in membrane permeate. The method limit of quantitation was 0.1 ng/L TBBPA. Sorption of TBBPA to fresh mixed-liquor suspended solids (MLSS) from a membrane bioreactor (MBR) were studied. In a kinetic study, sorption was found to be essentially complete after 12 hours of exposure to MLSS. Log Koc and log Kd were measured at 4.7 ± 0.8 and 1.9 ± 0.8 respectively (n = 22). These values were much higher than modelled estimates based on Kow (p ≥ 0.05), and higher than modelled estimates based on Kow and pKa (p ≥ 0.05). Data was successfully modelled using the Freundlich isotherm, having a Kf value of 8.5 and an n value of 1.7. TBBPA adsorbed to borosilicate glassware, with a wall-loss coefficient (Kw) of 0.15 ± 0.1 (n ≥ 3). TBBPA levels in WWTP influent varied from 13 to 29 ng/L while effluent concentrations varied from 0 to 2.2 ng/L over the same period. Three pilot-scale membrane bioreactors (MBRs) removed less TBBPA during the same time period, though MBR removal was also significant (p ≥ 0.05). Increasing MBR sludge residence time (SRT) increased removal at the 86 % confidence interval (p = 0.14). A nitrifying MABR was shown to remove TBBPA significantly when spiked with ammonia and TBBPA (p ≥ 0.05), showing that nitrifying bacteria can degrade TBBPA. An MABR hollow fibre was found to adsorb TBBPA. Various soluble microbial products (SMP) were studied from MBRs fed munici- pal influent. Using current measurement practices, SMP were shown to be sensitive to matrix effects. Use of the standard addition technique (SA) can compensate for this. Measurements using SA showed SMP degrades rapidly during storage in the fridge and due to freezing. SA was also used to compare commonly used SMP extraction techniques, and showed that extraction method influences recovery.

Leaching and Transformation of Flame Retardants and Plasticizers under Simulated Landfill Conditions / Läckage och transformation av flamskyddsmedel och mjukgörare under simulerade deponiförhållanden

Hörsing, Maritha January 2008 (has links)
Many products used in our everyday life contain chemicals added to give them specific properties. Flame retardants (FRs) are added to prevent or retard fires in textiles, plastics etc., while plasticizers are supplied to make plastics more flexible. Through their widespread applications chemicals from both groups are emitted and spread in the environment during usage and disposal. For a long time these products were mainly disposed of in landfills, and in many areas they still are. Thus, since some of these chemicals also pose potential environmental risks and health hazards, there is a need to elucidate their fates during exposure to the landfill environmentThe objectives of this thesis were to investigate the leaching and transformation of FRs and plasticizers from products in which they are used under simulated landfill conditions. To assess the importance of changes in these processes as landfills progress through recognised ageing phases (accompanied by large transitions in both physico-chemical and biological conditions) it was desirable to simulate the changes that typically occur in landfills within a short time period, of 1-2 years.. This was achieved using the newly developed intermediate-scale (3 litre) Modular Environmental Test System (METS).The METS were employed in two studies. The first was an investigation of the leaching and degradation of plasticizers from PVC carpet material incubated at different temperatures (20, 37, 55 and 70°C) prevailing in landfills. Plasticizers subjected to this investigation were the phthalates di-2-ethylhexyl phthalate (DEHP) and benzyl-butyl phthalate (BBP), both of which were found to leach from the carpet. The leaching of DEHP and BBP generally increased with increases in the incubation temperature. However, the most rapid leaching of BBP occurred at 37°C, probably due to high microbial activity at this temperature. Both DEHP and BBP were shown to be degraded within the landfill environment and the degradation potential was highest during the methanogenic landfill phase. In the second METS study the leaching of FRs used in both reactive and additive applications (i.e. chemically bonded to and merely blended with the material, respectively) was characterised. The epoxy oligomer tetrabromobishpenol A (TBBPA) and the phosphorus-based Pyrovatex FRs were selected as representatives for the reactive FRs, while the nitrogen-based melamine and phosphorus-based Proban FRs were selected to represent additive classes. During the incubations, which lasted more than two years, the leaching from melamine was shown to be affected by the landfill phase development. The leaching from the Pyrovatex-treated material and the TBBPA epoxy oligomer seemed to result almost entirely from the washout of unreacted manufacturing residuals. This was also probably true for the FR in the Proban-treated material, although it is durable (despite being additively applied) and thus seemed to leach more slowly (manifested as an increase in phosphate levels in the leachate towards the end of the monitoring period).Finally, due to the paucity of knowledge regarding the fate of ether derivatives of TBBPA (which are also used as FRs) an anaerobic degradation assay was performed. The method employed for this assay was a modified, small-scale ISO standard method. In order to evaluate the degradation assay a uniform analytical protocol was developed. The degradation survey showed that losses of TBBPA, TBBPA-dimethyl ether and bisphenol A dimethyl ether occurred, but no losses of the most hydrophobic compound, TBBPA-dibromopropyl ether, were observed. / Många av de varor och produkter vi kommer i kontakt med dagligen innehåller kemikalier, som tillsats för att materialen i produkterna skall få specifika egenskaper. Till dessa sk funktionella kemiska föreningar hör till exempel flamskyddsmedel och mjukgörare. Den förra förhindrar att produkter fattar eld eller minskar omfattningen av brand. Mjukgörare ingår fr a i plaster för att dessa skall bli smidiga och formbara. Eftersom stora mängder av dessa substanser används eller har använts i produkter i samhället har de spridits till många miljöer. Produkterna hamnar ofta på soptipp, då de inte används mer eller är utnötta. Eftersom flera av dessa substanser innebär risk för hälsa och miljö, är det påkallat att utreda hur de beter sig i soptippsmiljön.Syftet med detta avhandlingsarbete är att undersöka eventuell frisättning och omvandling av dessa två typer av funktionella kemikalier i deponimiljö. Sedan tidigare vet man att sådan frisättning kan var starkt kopplad till åldern och därmed utvecklingen av den kemiska och fysiska miljön förändrats fr a genom tillväxten av mikroorganismer i soptippen. För att komma åt att studera frisättningen under de för deponier karakteristiska utvecklingsfaserna utvecklades en metod (Modualr Environmetal Test System; METS) för att simulera faserna över relativt kort tid (ca 1-2 år). I avhandlingen presenteras två studier, där METS utnyttjats: 1) Frisättning av mjukgörare från en PVC-matta i relation till temperaturer, som uppträder i soptippar (20-70oC) samt 2) Läckage av olika flamskyddsmedel i reaktiv respektive additiv användning studerades för olika applikationer. Vid reaktive applikation är flamskyddsmedlet kovalent bundet till polymeren i produktmaterialet, medan det additivt använda flamskyddsmedlet är inblandat i materialet.Två ftalater (di-2-etylhexyl ftalat, DEHP och bensyl-butyl ftalat (BBP), visade sig läcka från mattan, vilket ökade med högre temperature. De frisattes dock som mest vid 37oC, vilket sannolikt beror på den höga mikrobiella aktiviteten vid denna temperatur. Båda ftalterna bröts ned i soptippsmiljön och hastigheten var störst i den metanogena fasen.En epoxyoligomer (tetrabromobishpenol A TBBPA) och Pyrovatex, som bygger på en fosforförening, användes som modeller för reaktiva flamskyddsmedel. Melamin, som klassas som ett kvävebaserat flamskyddsmedel, fick tillsammans med Proban (fosforbaserat) represen-tera de som används additivt. Medan en frisättning av melamin kunde relateras till utvecklingen av deponimiljön simulerad i METS, så verkar den observerade frisättningen av kemikalierna från de reaktivt behandlade Pyrovatexmaterialet och från epoxipolymeren TBBPA förr ha en fysikalisk-kemisk grund oberoende av utvecklingsfaserna i tippmodel-lerna. Flamskyddsmedlen tvättades helt enkelt ut ur de behandlade produkterna. Probanbehandlingen, som motstår förhållandevis många tvättar trots att det används additivt, visade sig läcka långsamt utan en direkt koppling till fasutvecklingen i METS.Kunskaperna om vad som händer med TBBPA:s eterderivat i deponier är i stort sett obefintliga. Flera av dessa derivat används också som flamskyddsmedel. Därför genomfördes en anaerob nedbrytningsstudie av dessa substanser. För att kunna göra denna studie behövdes en omfattande anpassning och utveckling av metodik, vilket resulterade i ett nytt protokoll för analys av dessa ämnen i olika matriser. Studien visade minskning av koncentrationerna av TBBPA, TBBPA-dimetyleter och bisfenol A dimetyl eter, vilket kan tas som ett tecken på att en transformation och/eller nedbrytning skett. Då dessa föreningar kan omvandlas till mer toxiska substanser bör de undersökas vidare.

Persistency, bioaccumulation and toxicity assessment of selected brominated flame retardants

Rattfelt Nyholm, Jenny January 2009 (has links)
Brominated flame retardants (BFRs) are chemicals used in e.g. electronic equipment, textiles and plastics for the prevention of fire. Over recent decades, concern has been raised regarding some heavily used BFRs, since the levels in the environment have been increasing. In the present thesis, persistent, bioaccumulative, and toxic (PBT) properties were studied for a structurally varied set of BFRs selected to represent more than 60 organic BFRs. The studied BFRs include: 2,4,4'-tribromodiphenyl ether (BDE 28), 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE  183), decabromodiphenyl ether (BDE 209), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), tetrabromobisphenol A 2-hydroxyethyl ether (TBBPA OHEE), 2,4,6-tribromophenol (246BrPh), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), and hexabromobenzene (HxBrBz). It is likely that soil will act as a sink for BFRs. Therefore, studies of BFRs were performed on persistence in soil, and on bioaccumulation from soil in the earthworm Eisenia fetida. Large variation in the biodegradability in soil among the tested BFRs was observed. The studied brominated diphenyl ethers (BDE 28 and BDE 209) were very persistent under both aerobic and anaerobic conditions, while 246BrPh and TBECH degraded quickly in both aerobic and anaerobic soil. The bioaccumulation in earthworm from soil was high for HxBrBz, TBECH and for tested brominated diphenyl ethers with 4-6 bromine atoms (BDE 47, BDE 99, and BDE 153). Bioaccumulation was also studied in zebrafish after dietary exposure to a mixture of BFRs. It was shown that several metabolites were formed and retained in zebrafish, which highlights the importance of also searching for and identifying persistent degradation products. Maternal transfer was shown for all BFRs present in the female zebrafish. This shows that zebrafish young (fry) are exposed to these BFRs at approximately the same concentrations as female zebrafish during the early-life stages, when fish are usually most sensitive to organic contaminants. Toxicity of individual BFRs and a BFR mixture was studied in Nitocra spinipes using a silica gel-based system. Highest toxicities were observed for BDE 28, TBBPA, and TBBPA OHEE. In the mixture toxicity study, simultaneous exposure to low concentrations (individually causing no significant effect) of six BFRs significantly affected the survival of Nitocra spinipes. The results from the PBT studies presented in the thesis and literature data were compared with the criteria for PBT classification, as set in the European REACH legislation. Further, some BFRs with physico-chemical properties similar to those of identified PBTs were suggested to be prioritized for future PBT testing.

Association between Immunological Reactivity with Tetrabromobisphenol-A and Autoimmune Target Sites of the Nervous System

Kharrazian, Datis 01 January 2018 (has links)
Tetrabromobisphenol-A (TBBPA) is the most widely used flame retardant. Flame retardants are sprayed on furniture, mattress beds, children’s pajamas, car seats, upholstery, carpets, and rugs in the United States. Chemical immune reactivity may play a role in the epidemic of autoimmune disease. The goal of this research is to investigate whether any correlation exists between immunological reactivity to TBBPA, a key chemical used in most flame retardants, and neurological autoimmune target sites that are associated with neurological autoimmune diseases with a diverse and specific list of antibodies that include myelin basic protein, myelin-associated glycoprotein, alpha-synuclein, aquaporin receptors, and S100B antibodies with human serum samples. The outcomes of this research can be used to support the development of safety regulations and for identifying potential health concerns for current mandatory flame-retardant legislation. Additionally, this research may support the decisions made in respect of those suffering from neurological autoimmune diseases, as to whether removing flame retardant chemicals is a factor for consideration.

Retardéry hoření a jejich průnik do terestrického ekosystému / Flame retardants and their penetration into the terrestrial ecosystem

Chytil, Václav January 2014 (has links)
This diploma thesis was focused on the analysis of four compounds from brominated flame retardants group, namely pentabromoethylbenzene, hexabromocyclododecane, hexabromobenzene and tetrabromobisphenol A. Matrices were represented by four soil samples and four seat of fire samples. In addition, bisphenol A was also determined. First of all, process of extraction of analytes from matrices was optimized. Three different extraction techniques were tested (pressurized solvent extraction, microwave-assisted extraction and ultrasound-assisted extraction). Next step was to verify stability of target compounds in strongly acidic conditions and to optimize clean-up of extract by column chromatography. Gas chromatography with electron capture detection (GC-ECD) was chosen as an appropriate analytical method for the determination of brominated flame retardants. Bisphenol A was determined by gas chromatography with mass spectrometric detection (GC-MS). The derivatization of phenolic analytes before their final analytical determination was also essential.

New methods for determination of airborne pollutants : Focus on tetrabromobisphenol A, organophosphate triesters and polycyclic aromatic hydrocarbons

Tollbäck, Johanna January 2009 (has links)
The work presented in this thesis concerns the development and evaluation of new methods of sampling and analysis of organic pollutants in the indoor and outdoor environment. In Paper I, the development of a new method was reported for the determination of the brominated flame retardant tetrabromobisphenol A (TBBPA) in air using sampling with glass fiber filter and polyurethane foam (PUF), ultrasonic solvent extraction and liquid chromatography coupled to electrospray ionisation mass spectrometry (LC-ESI/MS). The MS fragmentation mechanism of TBBPA was thoroughly investigated and different acquisition modes were evaluated to achieve the most sensitive and selective detection. In Papers II and III, the potential use of Empore SPE membranes was evaluated for air sampling of volatile, semi-volatile and particle-associated organic compounds. Breakthrough studies conducted for 24h at air flows of 10- 20 L/min showed that the SPE membranes efficiently retains volatile and semi-volatile organophosphate esters and particles >10 nm. Effort was invested in the development of fast and environmental friendly methods, with low cost, for sample clean up and analysis. In Paper II, the sample preparation technique was dynamic solvent extraction with methanol coupled to LC-ESI/MS. The total run time per sample, including both extraction and separation, was less than 34 min, consuming only 1.6mL methanol. In Paper III, efficiency of selective extraction of polycyclic aromatic hydrocarbons from particulate matter sampled with Empore SPE membranes, using dynamic subcritical water extraction (DSWE) was investigated. Acceptable recoveries of the investigated compounds from reference material (SRM 1649a) were achieved. In Paper IV, the application of dynamic solid phase micro-extraction (SPME) air sampling was evaluated using, gas chromatography/positive ion chemical ionisation (GC/PICI) and tandem-MS detection for the determination of organophosphate esters in work environment.

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