En la present tesi doctoral s’han estudiat diversos mètodes per a l’eliminació de contaminants orgànics persistents en olis de peix amb finalitat alimentària. S’han posat al punt les metodologies d’anàlisi necessàries per a la correcta determinació d’aquests compostos en la matriu d’estudi. S’han avaluat amb detall les etapes de purificació de la mostra, fraccionament dels analits i anàlisi instrumental. El mètode ha estat validat amb resultats satisfactoris, i s’ha comprovat el seu bon funcionament a través de la participació en diversos exercicis d’intercalibtage, així com la realització de diversos estudis amb mostres reals d’oli de peix. S’ha estudiat l’eliminació dels contaminants orgànics persistents a través d’adsorbents sòlids amb base silícica i carbonàcia. Les condicions experimentals han estat estudiades més a fons mitjançant dissenys d’experiències, per acabar optimitzant el mètode d’adsorció amb un disseny d’evolució. Els millors resultats s’han obtingut amb el carbó actiu, que mostra una elevada eficàcia en l’eliminació de PCDD/Fs, d-l PCBs i HCB. S’ha estudiat l’eliminació dels contaminants orgànics persistents mitjançant tècniques de degradació fotoquímiques. Inicialment s’ha fotodegradat cada família de contaminants per separat, per poder estudiar més a fons les condicions necessàries per la seva eliminació, així com els seus mecanismes i productes de degradació. Posteriorment s’ha estudiat la fotodegradació simultània dels analits d’interès en oli de peix. Aquesta tècnica s’ha mostrat efectiva en l’eliminació de DDT, PBDEs, HCB i PCBs similars a dioxines. Paral•lelament als estudis d’eliminació mitjançant adsorbents sòlids i tècniques fotoquímiques, s’ha comprovat la qualitat dels olis de peix abans i després del tractament. El procés d’adsorció en sòlids no afecta significativament a la qualitat de l’oli, mentre que les tècniques fotoquímiques degraden una part dels àcids grassos insaturats. S’ha estudiat l’eliminació de contaminants orgànics persistents en oli de peix mitjançant la combinació de les dues tècniques estudiades anteriorment, amb una primera etapa de degradació fotoquímica i una segona etapa d’adsorció. S’han comparat els resultats finals d’eliminació que s’obtenen amb cada un dels mètodes desenvolupats (adsorció, fotodegradació i combinat). L’adsorció en carbó actiu és el procés més adequat per l’eliminació de COPs en oli de peix. S’ha realitzat un estudi dels nivells diastereomèrics i enantiomèrics d’un contaminant emergent -l’hexabromociclododecà (HBCD)- en oli de peix. S’ha avaluat la seva eliminació de la matriu d’estudi mitjançant adsorbents amb base carbonàcia i degradació fotoquímica, sent principalment eliminat per aquesta segona via. / En la presente tesis doctoral se han estudiado diversos métodos para la eliminación de contaminantes orgánicos persistentes en aceites de pescado con finalidad alimentaria. Se han desarrollado los métodos de análisis necesarios para la correcta determinación de estos compuestos en la matriz de estudio. Se han evaluado con detalle las etapas de purificación de la muestra, fraccionamiento de los analitos y análisis instrumental. El método ha sido validado con resultados satisfactorios, y se ha comprobado su buen funcionamiento mediante ejercicios de intercalibraje, así como la realización de diversos estudios con muestras reales de aceite de pescado. Se ha estudiado la eliminación de los contaminantes persistentes mediante adsorbentes sólidos con base silícica y carbonacea. Las condiciones experimentales han estado estudiadas en profundidad mediante diseños de experiencias y de evolución. Los mejores resultados se han obtenido con carbón activo, que demuestra una elevada eficacia en la eliminación de PCDD/Fs, dl-PCBs y HCB. Se ha estudiado la eliminación de los contaminantes orgánicos persistentes mediante técnicas de degradación fotoquímica. Inicialmente se ha fotodegradado cada familia de contaminantes por separado, para poder estudiar más a fondo las condiciones necesarias para su eliminación. Posteriormente se ha estudiado la degradación simultánea de los analitos de interés en aceite de pescado. Esta técnica se ha mostrado efectiva en la eliminación de DDT, PBDEs, HCB y PCBs similares a dioxinas. Paralelamente a los estudios de eliminación mediante adsorbentes sólidos y técnicas fotoquímicas, se ha comprobado la calidad de los aceites de pescado antes y después del tratamiento. El proceso de adsorción en sólidos no afecta significativamente a la calidad del aceite, mientras que las técnicas fotoquímicas degradan una parte de los ácidos grasos insaturados. Se ha estudiado la eliminación de contaminantes orgánicos persistentes en aceites de pescado mediante la combinación de las dos técnicas estudiadas anteriormente, con una primera etapa de degradación fotoquímica y una segunda etapa de adsorción. Se han comparado los resultados finales de eliminación que se obtienen con cada uno de los métodos desarrollados. La adsorción en carbón activo es el proceso más adecuado para la eliminación de COPs en aceite de pescado. Se ha realizado un estudio de los niveles diastereoisoméricos y enantioméricos de un contaminante emergente –HBCD- en aceite de pescado. Se ha evaluado su capacidad de eliminación de la matriz de estudio mediante adsorbentes con base carbonacia y degradación fotoquímica, siendo principalmente eliminado por la segunda vía. / During the present doctoral thesis several methods for the elimination of persistent organic pollutants from fish oil have been studied. Analytical methodologies for the determination of these compounds in fish oil have been developed. Sample purification, fractionation of the analytes and instrumental determination steps have been deeply studied. The method has been validated with satisfactory results, and its performance has been verified through its participation in several intercalibration exercises and studies with real fish oil samples. Elimination of persistent organic pollutants with silicon and carbon-based adsorbents has been studied. The experimental conditions have been studied in depth with an experimental design, to finally optimize the adsorption method using an evolutionary design. Best results have been obtained with the active carbon, showing high efficiency of the removal of PCDD/Fs, dioxin-like PCBs and HCB. Elimination of persistent organic pollutants with photochemical degradation techniques has been studied. Initially, each family of pollutants has been photodegraded separately, to determine its degradation conditions, as well as degradation mechanisms and by-products. Later, simultaneous photodegradation of the analytes has been studied in fish oil. This technique has shown high efficiency on the degradation of DDT, PBDEs, HCB and dioxin-like PCBs. The quality of the oils before and after the treatments with solid adsorbents and photochemical degradation has also been studied. The adsorption process does not significantly affect the quality of the oils, while photochemical techniques can degrade the unsaturated fatty acids. Elimination of persistent organic pollutants in fish oil combining adsorption in solids and photochemical degradation has been studied. Results obtained with each of the developed methodologies (adsorption, photodegradation and combined method) were compared. Adsorption in active carbon is the most suitable process for COPs elimination in fish oil. Finally, diastereoisomeric and enantiomeric levels of an emerging pollutant –hexabromocyclododecane (HBCD)- in fish oil have been studied. Its elimination has been evaluated with carbon-based adsorbents and photochemical degradation, being mainly eliminated with the photodegradation techniques.

The thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) is a major problem in waste incineration. Ideally, rather than relying on air cleaning systems and treatment techniques, their formation should be minimized or, if possible eliminated. The work presented in this thesis was conducted to obtain a deeper understanding of the thermal formation of PCDDs, PCDFs, PCBs, and PCNs during incineration using a 5 kW laboratory scale incinerator and two artificial wastes that were designed to reflect regional differences in waste composition. The first part of the thesis focuses on the validation of a recently-developed flue-gas sampling probe with enhanced cooling capabilities. Artifact formation of PCDDs and PCDFs can occur during the sampling of hot flue gases if the cooling is insufficient. The new probe was successfully used to collect samples at 700 °C without biasing the measured POP levels. The thermal formation of PCDDs, PCDFs, PCBs, and PCNs in the post-combustion zone of the incinerator was then studied by collecting flue gas samples at 400 °C, 300 °C, and 200 °C during the incineration of the two artificial wastes. Highly chlorinated POPs were formed in larger quantities when burning the waste with the higher content of metals and chlorine, which suggests that high metal levels in the waste favor the chlorination of less chlorinated POPs or otherwise facilitate the formation of highly chlorinated polyaromatics, possibly via the condensation of highly chlorinated phenols. The concentrations of these pollutants and the abundance of highly chlorinated homologues increased as the flue gas cooled. Fly ash particles play an important role in thermal POP formation by providing essential elements (carbon, chlorine, etc.) and catalytic sites. The chemical and mineralogical properties of fly ash samples were studied by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), and X-ray photoelectron spectroscopy (XPS) to determine their impact on thermal POP formation. Orthogonal Partial Least Squares (OPLS) modeling was used to identify correlations between the observed POP distributions and the physicochemical data. This investigation provided new insights into the impact of fly ash chemistry on thermal POP formation. In addition, the POP isomer distribution patterns generated during waste combustion were examined. These patterns are used to “fingerprint” mechanisms of POP formation. It was found that wastes containing large quantities of metals and chlorine favored the formation of highly chlorinated homologues including the very toxic 2,3,7,8-congeners. The data suggest that reducing fly ash emissions might increase the SO2 content of the flue gas and thereby suppress the Deacon process and the formation of harmful highly chlorinated aromatic species.

South Africa ratified the Stockholm Convention (SC), which became legally binding on 17 May 2004. This Convention targets 12 particularly toxic persistent organic pollutants (POPs) for virtual elimination. The Convention also requires parties to reduce the release of organochlorine pesticides and the intentionally- and unintentionally-produced POPs such as dioxins, furans and polychlorinated biphenyls (PCBs) (referred to as dioxin-like chemicals). Dioxins are a heterogeneous mixture of chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) congeners. These substances were never intentionally produced but are produced as by-products of industrial processes (such as metallurgical processes and bleaching of paper pulp). They can also be formed during natural processes such as volcanic eruptions and forest fires. The largest contributor to releases of PCDD/Fs in the environment is incomplete combustion from waste incinerators leading to the unintentional production of these compounds. Polychlorinated biphenyls (PCBs) are used in transformers and capacitors, but can also be formed unintentionally during industrial and thermal processes. Dioxin-like chemicals (PCDD/Fs and/or PCBs) are classified as persistent because of the following characteristics: lipophilicity and hydrophobicity; resistance to photolytic, chemical and biological degradation and they are able to travel long distances. As South Africa is a semiarid region, POPs will be less prone to travel here because these substances favour colder regions with high soil organic matter. Fish, predatory birds, mammals (including humans) absorb high concentrations of POPs through the process of bio-concentration, leading to bio-accumulation of these substances in the fatty tissue. PCDD/Fs occur as unwanted trace contaminants in air, water, land, in residues and products (such as consumer goods e.g. paper and textiles). The distribution of these chemicals into various matrices is problematic since they cause damage to the environment and human health. These chemicals pose a threat to human health when found in high concentrations that may lead to acute hepatoxicity and dermal toxicity (chloracne). Long-term exposure to low concentrations of these substances might lead to chronic effects such as reproductive problems and carcinogenicity. Since ferrous and non-ferrous metal production is a source of dioxin-like chemicals, a platinum mine in the Limpopo Province, South Africa, was selected for this investigation. The aim of the study was to determine if there are dioxin-like chemicals associated with platinum mining and processing, and if the H4IIE reporter gene bio-assay could be used to semi-quantify and assess the potencies of the complex environmental and process samples by determining their Toxic Equivalency Quotients (TEQ). The implications of the sources to the formation of dioxin-like chemicals regarding the SC were investigated and recommendations were made to improve this study. Samples were collected from tailings dams, woodchips, a dumpsite and slag from the smelter at Union Section. Samples were extracted with the Soxhlet apparatus using hexane as solvent. The percentage total organic carbon (%TOC) was determined for each sample to normalise the data. The method used was the Walkley-Black method. In determining the TEQ of each sample, the H4IIE luc cell line was used. The cells of the H4IIE luc line are genetically modified rat hepatoma cells stably transfected with a luciferase firefly gene. The luciferase gene is activated by the presence of dioxin-like compounds and the concentration of the enzyme is measured as relative light units (RLUs). The amount of RLUs is directly proportional to the dioxin load in the extract. This method is rapid, cost and time-effective in determining the TEQ when compared to chemical analysis. The TEQ2o-valuesin the various samples, as determined with the H4IIE luc cell line, ranged from 0.007 ngTEQ/kg to 54.06 ngTEQ/kg. Thermal processes at the smelter, sorption of hydrophobic organic compounds (HOCs) to soil and tailings, and external sources such as anthropogenic activities contributed to high TEQ2o-values. Climatic conditions, wind, precipitation, and solubility of HOCs into surfactants lead to low TEQ20. The smelter at Union Section had a very high TEQ20of 44.62 ngTEQ/kg compared to Impala Platinum mine (5.15 ngTEQ/kg). This implies that workers at Union Section are possibly exposed to low and high concentrations of dioxin-like chemicals. Long-term exposure to these compounds could lead to bio-accumulation in the fatty tissue of the mine workers, leading to chronic effects such as reproductive problems and cancer. The air emission of the furnace at the smelter was 0.03 gTEQ/annum and the release of the PCDD/Fs into the slag was 0.60 gTEQ/annum. By effectively managing the smelter it is possible to reduce the TEQ. The TEQ of each sample increased due to normalising the data. The normalised TEQ20 ranged from 0.94 ng TEQ/kg to 42497.48 ngTEQ/kg. Dioxin-like chemicals are present on a platinum mine, but at varying quantities and the effects of these compounds might be detrimental to the environment and the workers at the platinum mine. Further analyses of the health impacts associated with the platinum mine are needed. The H4IIE reporter gene bio-assay could be used to effectively determine the TEQ of each sample. Although this investigation has identified the formation and presence of dioxin-like chemicals at certain stages of mining and processing, not all of the processes were investigated. Some of these processes have the potential to add, and even destroy, these chemicals, affecting potential human exposure and amounts released to the environment. This, however, requires further investigation. The financial assistance of the National Research Foundation (NRF) towards this research is hereby acknowledged. Opinions expressed and conclusions arrived at, are those of the author and are not necessarily to be attributed to the NRF. / Thesis (M. Environmental Science)--North-West University, Potchefstroom Campus, 2006.

Photoinduced electron transfer is a fundamentally interesting process; it occurs everywhere in the natural world. Studies on electron transfer shed light on questions about the interaction between molecules and how the dynamics of these can be utilized to steer the electron transfer processes to achieve a desired goal. The goal may be to get electrons to the electrode of a solar cell, or to make the electrons form an energy rich fuel such as hydrogen, and it may also be an input or output for molecular switches. The importance of electron transfer reactions will be highlighted in this thesis, however, the main motivation is to gain a better understanding of the fundamental processes that affect the rate and direction of the electron transfer. A study of photoinduced electron transfer (ET) in a series of metallophorphyrin/bipyridinium complexes in aqueous solution provided fresh insight concerning the intimate relationship between vibrational relaxation and electron transfer. The forward electron transfer from porphyrin to bipyridinium as well as the following back electron transfer to the ground state could be observed by femtosecond transient absorption spectroscopy. Both the reactant and the product states of the ET processes were vibrationally unrelaxed, in contrary to what is assumed for most expressions of the ET rates. This could be understood from the observation of unrelaxed ground states. The excess energy given by the initial excitation of the porphyrin does not relax completely during the two steps of electron transfer. This is an unusual observation, not reported in the literature prior the studies presented in this thesis. This study also gave the first clear evidence of electronically excited radical pairs formed as products of intramolecular electron transfer. Signs of electronically excited radical pairs were seen in transient spectra, and were further verified by the observation that the rates followed a Marcus normal region behavior for all excitation wavelengths, despite the relatively large excess energy of the second excited state. This thesis also concerns electron transfer in solar cell dyes and mixed valence complexes. In the ruthenium polypyridyl complex Ru(dcb)2(NCS)2, where dcb = 4,4’-dicarboxy-2,2’-bipyridine, inter-ligand electron transfer (ILET) in the 3MLCT state was followed by means of femtosecond transient absorption anisotropy that was probed in the mid-IR region. Unexpectedly, ILET was not observed because electron density was localized on the same bpy during the time-window allowed by the rotational lifetime.

Farmed Southern Bluefin Tuna (SBT) (Thunnus maccoyii) is an important export product for South Australia (SA). It is exported to Japan, China, Korea and the United States for the sushi and sashimi markets. The primary purpose of SBT farming in SA is to fatten wild-caught juvenile fish (2-4 years of age with initial mean weights between 12-20 kg) over a period of approximately five months by feeding a selection of baitfish types. Farmers, farm managers and consumers of SBT all have an interest in managing chemical residues that have the potential to biomagnify in the fatty tissue of the farmed SBT fillets. Of particular interest are chemical residues of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins / dibenzofurans (PCDD/Fs). This research presents the investigations and experimental validation of a predictive model that can be used to address the levels of residues in the fillets of farmed SBT at harvest from feeding (as the source) when applied to SBT aquaculture. An additional industry-focussed aim of this research was to determine if a Longer Term Holding (LTH) farming period, with a duration of an extra 12 months after a typical farming period of approximately five months, could produce SBT with higher condition index (CI) and lipid content, while keeping levels of PCBs and PCDD/Fs low, compared to the typical farming period. The justification for this research is that an adequate quantitative model is essential to help industry achieve targeted concentrations in the final fillet product by making scientific-based decisions on baitfish selection (baitfish strategies for the feeding of SBT), and longer term, to confidently demonstrate to local markets and importing countries that Australia is actively managing levels of PCBs and PCDD/Fs in farmed SBT, to ensure a high quality and safe product is delivered to the consumer. The novelty of this research is underpinned by four integrated stages, and the criteria for an adequate model established. The important criteria included: accurate predictions versus observed data demonstrated through the analysis of residual plots, potential physiological interpretation of model coefficients, parsimony – the model should be as simple as possible (but no simpler) and that the model should be easy to use. Firstly, a logical starting point was the development of a risk framework for residues in SBT. The developed framework was based on conventional principles of microbiological risk assessment highlighted in Codex Alimentarius. The risk framework consists of five governing principles: hazard identification, hazard characterisation, exposure assessment, risk characterisation and model validation. The advantages of the risk framework is that it provides a systematic research approach and permits information to be handled unambiguously, especially important for the niche SBT industry where chemical residue research is carried out for the first time. Secondly, because of a lack of available scientific data in context of this research, commercial-scale experimental field data for levels of PCBs and PCDD/Fs in typical farmed SBT as affected by feeding and growth were collected over 17 months at seven time intervals from Farm Delta Fishing Pty Ltd in 2005/06 (n = 50). Field data from another commercial company, Farm Alpha Fishing Pty Ltd, was collected over the typical farming period specific to this company, spanning 15 weeks at three time intervals in 2006, for validation work (n = 15). The data obtained from Farm Delta Fishing Pty Ltd revealed that whole weight of farmed SBT increased from 18.5 kg to 30.3 kg for a typical farming period, and subsequently to 41.0 kg by the end of the LTH farming period. A maximum mean CI of 24.0 ± 0.5 kg.m⁻³ and a maximum mean lipid content of 17.6 ± 0.5% was achieved at the third time interval of the typical farming period, for the baitfish types and ratios used as feed. There were no significant differences in the CI and lipid between the final harvests of the typical farming and LTH periods, i.e. even after an additional 12 months of farming. PCB and PCDD/F concentrations, however, increased between the final harvests of the typical farming and LTH periods. The data indicated that a typical farming period was sufficient to achieve a maximum CI and lipid content with lower concentrations of PCBs and PCDD/Fs in the fillets relative to the LTH farming period. For the third stage of this research, a quantitative model was synthesised and applied to the PCB and PCDD/F (2,3,7,8-TeCDF) data detected in farmed SBT fillets. Assimilation efficiencies for PCBs and 2,3,7,8-TeCDF in the fillets of SBT were obtained. An assimilation efficiency, or percentage retention (efficiency expressed as a percentage), in the fillet of SBT is a measure of the uptake of a chemical residue from food (baitfish) to the SBT fillet. For the WHO-PCBs, assimilation efficiencies based on SBT fillets ranged between 19.1 – 35.3 % with the exception of PCB 169. The highest assimilation efficiency of 35.3 %, with a range of 30.4 – 40.3 % (at the 95 % confidence level) was attributed to the most toxic PCB congener, PCB 126. An assimilation efficiency of 39.2 % was determined in SBT fillets for the congener 2,3,7,8-TeCDF, which was higher than the assimilation efficiencies determined for the WHO-PCB congeners. A residual plot as predicted value versus observed value indicated that the predictive model was neither under- or over-parameterised. However, when the predictive model was assessed against the data set from Farm Alpha Pty Ltd, the model over-predicted the actual PCB and PCDD/F concentrations. The over-prediction is attributed to possible overfeeding of SBT farmed by Farm Alpha Fishing Pty Ltd. From a food safety point of view, in the absence of ideal predictions because of a lack of ideal validation data sets, an over-prediction instead of under-prediction is preferred. In the fourth stage, the practical application of the predictive model was demonstrated. Because SBT fillets are retailed as tissue group-specific, i.e. akami (low fat), chu-toro (medium fat) and otoro (high fat) fillets, PCB and PCDD/F analyses were carried out on the three tissue groups for selected SBT (n = 7). Dietary modelling on SBT consumption in humans was carried out using findings from the predictive model and tissue-specific data. The baitfish strategy employed for the feeding of farmed SBT consequently affects dietary exposure to SBT consumers. Exposure to PCBs and PCDD/Fs is approximately seven times lower for the consumption of a skin-free, boneless akami fillet than for a comparable otoro fillet of the same size. This dietary exposure assessment accounted only for consumption of SBT tissue-specific fillets. The experimental field study and modelling work on PCB and PCDD/F concentrations in farmed SBT (fillets) outlined in this thesis importantly directs the need to re-evaluate a specific model to better cater for SBT farming practices where SBT fillets are produced for human consumption. Because conditions that normally pertain to commercial farming of wild-caught fish were studied, findings should be of interest to industries where other species of fish (for food) are farmed in sea-cages in the open ocean. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1342453 / Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering, 2008

Farmed Southern Bluefin Tuna (SBT) (Thunnus maccoyii) is an important export product for South Australia (SA). It is exported to Japan, China, Korea and the United States for the sushi and sashimi markets. The primary purpose of SBT farming in SA is to fatten wild-caught juvenile fish (2-4 years of age with initial mean weights between 12-20 kg) over a period of approximately five months by feeding a selection of baitfish types. Farmers, farm managers and consumers of SBT all have an interest in managing chemical residues that have the potential to biomagnify in the fatty tissue of the farmed SBT fillets. Of particular interest are chemical residues of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins / dibenzofurans (PCDD/Fs). This research presents the investigations and experimental validation of a predictive model that can be used to address the levels of residues in the fillets of farmed SBT at harvest from feeding (as the source) when applied to SBT aquaculture. An additional industry-focussed aim of this research was to determine if a Longer Term Holding (LTH) farming period, with a duration of an extra 12 months after a typical farming period of approximately five months, could produce SBT with higher condition index (CI) and lipid content, while keeping levels of PCBs and PCDD/Fs low, compared to the typical farming period. The justification for this research is that an adequate quantitative model is essential to help industry achieve targeted concentrations in the final fillet product by making scientific-based decisions on baitfish selection (baitfish strategies for the feeding of SBT), and longer term, to confidently demonstrate to local markets and importing countries that Australia is actively managing levels of PCBs and PCDD/Fs in farmed SBT, to ensure a high quality and safe product is delivered to the consumer. The novelty of this research is underpinned by four integrated stages, and the criteria for an adequate model established. The important criteria included: accurate predictions versus observed data demonstrated through the analysis of residual plots, potential physiological interpretation of model coefficients, parsimony – the model should be as simple as possible (but no simpler) and that the model should be easy to use. Firstly, a logical starting point was the development of a risk framework for residues in SBT. The developed framework was based on conventional principles of microbiological risk assessment highlighted in Codex Alimentarius. The risk framework consists of five governing principles: hazard identification, hazard characterisation, exposure assessment, risk characterisation and model validation. The advantages of the risk framework is that it provides a systematic research approach and permits information to be handled unambiguously, especially important for the niche SBT industry where chemical residue research is carried out for the first time. Secondly, because of a lack of available scientific data in context of this research, commercial-scale experimental field data for levels of PCBs and PCDD/Fs in typical farmed SBT as affected by feeding and growth were collected over 17 months at seven time intervals from Farm Delta Fishing Pty Ltd in 2005/06 (n = 50). Field data from another commercial company, Farm Alpha Fishing Pty Ltd, was collected over the typical farming period specific to this company, spanning 15 weeks at three time intervals in 2006, for validation work (n = 15). The data obtained from Farm Delta Fishing Pty Ltd revealed that whole weight of farmed SBT increased from 18.5 kg to 30.3 kg for a typical farming period, and subsequently to 41.0 kg by the end of the LTH farming period. A maximum mean CI of 24.0 ± 0.5 kg.m⁻³ and a maximum mean lipid content of 17.6 ± 0.5% was achieved at the third time interval of the typical farming period, for the baitfish types and ratios used as feed. There were no significant differences in the CI and lipid between the final harvests of the typical farming and LTH periods, i.e. even after an additional 12 months of farming. PCB and PCDD/F concentrations, however, increased between the final harvests of the typical farming and LTH periods. The data indicated that a typical farming period was sufficient to achieve a maximum CI and lipid content with lower concentrations of PCBs and PCDD/Fs in the fillets relative to the LTH farming period. For the third stage of this research, a quantitative model was synthesised and applied to the PCB and PCDD/F (2,3,7,8-TeCDF) data detected in farmed SBT fillets. Assimilation efficiencies for PCBs and 2,3,7,8-TeCDF in the fillets of SBT were obtained. An assimilation efficiency, or percentage retention (efficiency expressed as a percentage), in the fillet of SBT is a measure of the uptake of a chemical residue from food (baitfish) to the SBT fillet. For the WHO-PCBs, assimilation efficiencies based on SBT fillets ranged between 19.1 – 35.3 % with the exception of PCB 169. The highest assimilation efficiency of 35.3 %, with a range of 30.4 – 40.3 % (at the 95 % confidence level) was attributed to the most toxic PCB congener, PCB 126. An assimilation efficiency of 39.2 % was determined in SBT fillets for the congener 2,3,7,8-TeCDF, which was higher than the assimilation efficiencies determined for the WHO-PCB congeners. A residual plot as predicted value versus observed value indicated that the predictive model was neither under- or over-parameterised. However, when the predictive model was assessed against the data set from Farm Alpha Pty Ltd, the model over-predicted the actual PCB and PCDD/F concentrations. The over-prediction is attributed to possible overfeeding of SBT farmed by Farm Alpha Fishing Pty Ltd. From a food safety point of view, in the absence of ideal predictions because of a lack of ideal validation data sets, an over-prediction instead of under-prediction is preferred. In the fourth stage, the practical application of the predictive model was demonstrated. Because SBT fillets are retailed as tissue group-specific, i.e. akami (low fat), chu-toro (medium fat) and otoro (high fat) fillets, PCB and PCDD/F analyses were carried out on the three tissue groups for selected SBT (n = 7). Dietary modelling on SBT consumption in humans was carried out using findings from the predictive model and tissue-specific data. The baitfish strategy employed for the feeding of farmed SBT consequently affects dietary exposure to SBT consumers. Exposure to PCBs and PCDD/Fs is approximately seven times lower for the consumption of a skin-free, boneless akami fillet than for a comparable otoro fillet of the same size. This dietary exposure assessment accounted only for consumption of SBT tissue-specific fillets. The experimental field study and modelling work on PCB and PCDD/F concentrations in farmed SBT (fillets) outlined in this thesis importantly directs the need to re-evaluate a specific model to better cater for SBT farming practices where SBT fillets are produced for human consumption. Because conditions that normally pertain to commercial farming of wild-caught fish were studied, findings should be of interest to industries where other species of fish (for food) are farmed in sea-cages in the open ocean. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1342453 / Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering, 2008

Farmed Southern Bluefin Tuna (SBT) (Thunnus maccoyii) is an important export product for South Australia (SA). It is exported to Japan, China, Korea and the United States for the sushi and sashimi markets. The primary purpose of SBT farming in SA is to fatten wild-caught juvenile fish (2-4 years of age with initial mean weights between 12-20 kg) over a period of approximately five months by feeding a selection of baitfish types. Farmers, farm managers and consumers of SBT all have an interest in managing chemical residues that have the potential to biomagnify in the fatty tissue of the farmed SBT fillets. Of particular interest are chemical residues of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins / dibenzofurans (PCDD/Fs). This research presents the investigations and experimental validation of a predictive model that can be used to address the levels of residues in the fillets of farmed SBT at harvest from feeding (as the source) when applied to SBT aquaculture. An additional industry-focussed aim of this research was to determine if a Longer Term Holding (LTH) farming period, with a duration of an extra 12 months after a typical farming period of approximately five months, could produce SBT with higher condition index (CI) and lipid content, while keeping levels of PCBs and PCDD/Fs low, compared to the typical farming period. The justification for this research is that an adequate quantitative model is essential to help industry achieve targeted concentrations in the final fillet product by making scientific-based decisions on baitfish selection (baitfish strategies for the feeding of SBT), and longer term, to confidently demonstrate to local markets and importing countries that Australia is actively managing levels of PCBs and PCDD/Fs in farmed SBT, to ensure a high quality and safe product is delivered to the consumer. The novelty of this research is underpinned by four integrated stages, and the criteria for an adequate model established. The important criteria included: accurate predictions versus observed data demonstrated through the analysis of residual plots, potential physiological interpretation of model coefficients, parsimony – the model should be as simple as possible (but no simpler) and that the model should be easy to use. Firstly, a logical starting point was the development of a risk framework for residues in SBT. The developed framework was based on conventional principles of microbiological risk assessment highlighted in Codex Alimentarius. The risk framework consists of five governing principles: hazard identification, hazard characterisation, exposure assessment, risk characterisation and model validation. The advantages of the risk framework is that it provides a systematic research approach and permits information to be handled unambiguously, especially important for the niche SBT industry where chemical residue research is carried out for the first time. Secondly, because of a lack of available scientific data in context of this research, commercial-scale experimental field data for levels of PCBs and PCDD/Fs in typical farmed SBT as affected by feeding and growth were collected over 17 months at seven time intervals from Farm Delta Fishing Pty Ltd in 2005/06 (n = 50). Field data from another commercial company, Farm Alpha Fishing Pty Ltd, was collected over the typical farming period specific to this company, spanning 15 weeks at three time intervals in 2006, for validation work (n = 15). The data obtained from Farm Delta Fishing Pty Ltd revealed that whole weight of farmed SBT increased from 18.5 kg to 30.3 kg for a typical farming period, and subsequently to 41.0 kg by the end of the LTH farming period. A maximum mean CI of 24.0 ± 0.5 kg.m⁻³ and a maximum mean lipid content of 17.6 ± 0.5% was achieved at the third time interval of the typical farming period, for the baitfish types and ratios used as feed. There were no significant differences in the CI and lipid between the final harvests of the typical farming and LTH periods, i.e. even after an additional 12 months of farming. PCB and PCDD/F concentrations, however, increased between the final harvests of the typical farming and LTH periods. The data indicated that a typical farming period was sufficient to achieve a maximum CI and lipid content with lower concentrations of PCBs and PCDD/Fs in the fillets relative to the LTH farming period. For the third stage of this research, a quantitative model was synthesised and applied to the PCB and PCDD/F (2,3,7,8-TeCDF) data detected in farmed SBT fillets. Assimilation efficiencies for PCBs and 2,3,7,8-TeCDF in the fillets of SBT were obtained. An assimilation efficiency, or percentage retention (efficiency expressed as a percentage), in the fillet of SBT is a measure of the uptake of a chemical residue from food (baitfish) to the SBT fillet. For the WHO-PCBs, assimilation efficiencies based on SBT fillets ranged between 19.1 – 35.3 % with the exception of PCB 169. The highest assimilation efficiency of 35.3 %, with a range of 30.4 – 40.3 % (at the 95 % confidence level) was attributed to the most toxic PCB congener, PCB 126. An assimilation efficiency of 39.2 % was determined in SBT fillets for the congener 2,3,7,8-TeCDF, which was higher than the assimilation efficiencies determined for the WHO-PCB congeners. A residual plot as predicted value versus observed value indicated that the predictive model was neither under- or over-parameterised. However, when the predictive model was assessed against the data set from Farm Alpha Pty Ltd, the model over-predicted the actual PCB and PCDD/F concentrations. The over-prediction is attributed to possible overfeeding of SBT farmed by Farm Alpha Fishing Pty Ltd. From a food safety point of view, in the absence of ideal predictions because of a lack of ideal validation data sets, an over-prediction instead of under-prediction is preferred. In the fourth stage, the practical application of the predictive model was demonstrated. Because SBT fillets are retailed as tissue group-specific, i.e. akami (low fat), chu-toro (medium fat) and otoro (high fat) fillets, PCB and PCDD/F analyses were carried out on the three tissue groups for selected SBT (n = 7). Dietary modelling on SBT consumption in humans was carried out using findings from the predictive model and tissue-specific data. The baitfish strategy employed for the feeding of farmed SBT consequently affects dietary exposure to SBT consumers. Exposure to PCBs and PCDD/Fs is approximately seven times lower for the consumption of a skin-free, boneless akami fillet than for a comparable otoro fillet of the same size. This dietary exposure assessment accounted only for consumption of SBT tissue-specific fillets. The experimental field study and modelling work on PCB and PCDD/F concentrations in farmed SBT (fillets) outlined in this thesis importantly directs the need to re-evaluate a specific model to better cater for SBT farming practices where SBT fillets are produced for human consumption. Because conditions that normally pertain to commercial farming of wild-caught fish were studied, findings should be of interest to industries where other species of fish (for food) are farmed in sea-cages in the open ocean. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1342453 / Thesis (Ph.D.) -- University of Adelaide, School of Chemical Engineering, 2008

95 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-09-30T14:18:36Z No. of bitstreams: 1 Dissertação_Geovani.pdf: 923282 bytes, checksum: 410ba5c5697a7df386c4f1c432de6a27 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-09-30T14:20:24Z (GMT) No. of bitstreams: 1 Dissertação_Geovani.pdf: 923282 bytes, checksum: 410ba5c5697a7df386c4f1c432de6a27 (MD5) / Made available in DSpace on 2013-09-30T14:20:24Z (GMT). No. of bitstreams: 1 Dissertação_Geovani.pdf: 923282 bytes, checksum: 410ba5c5697a7df386c4f1c432de6a27 (MD5) Previous issue date: 2011 / CNPq / No presente trabalho, foram desenvolvidos métodos analíticos baseados em estratégias alternativas de preparo de amostras para a determinação de metais em alimentos por técnicas de espectrometria de absorção atômica com chama. No primeiro método, a amostragem de suspensão foi usada para o preparo de amostras de iogurte para a determinação de zinco por HR-CS FAAS. As condições experimentais estabelecidas para o preparo das suspensões foram: solução de HCl 2,0 mol L-1, tempo de sonicação de 20 min e uma massa de amostra de 1,0 g. Nestas condições, os limites de detecção e quantificação obtidos foram de 0,10 e 0,32 µg g-1, respectivamente. A precisão expressa como desvio padrão relativo (RSD) foi de 0,82 e 2,08% para amostras contendo concentrações de zinco de 4,85 e 2,49 µg g-1, respectivamente. A exatidão do método foi confirmada pela análise de material de referência certificado (CRM) de leite em pó desnatado NIST SRM 1549. O método proposto foi aplicado para determinação de zinco em sete amostras de iogurte. O teor de zinco variou de 2,19 a 4,85 µg g-1. No segundo método, a foto- oxidação com radiação UV e H2O2 foi usada para o preparo de amostras de vinho para a determinação de ferro e manganês por FS-FAAS. As condições experimentais estabelecidas para a degradação das amostras de vinho foram: volume de 2,5 mL de H2O2 30% (v/v), pH 10,0, concentração do tampão de 0,14 mol, L-1 e um tempo de irradiação de 30 min. Nestas condições, foram obtidos limites de detecção e quantificação de 0,030 e 0,099 µg mL-1 para ferro, e de 0,022 e 0,073 µg mL-1 para manganês, respectivamente. A precisão expressa como RSD foi de 2,8 e 0,65% para ferro, e de 2,7 e 0,54% para manganês para concentrações de 0,5 e 2,0 µg mL-1, respectivamente. Teste de adição e recuperação usado para avaliar a exatidão do método foi na faixa de 90 a 111% para ferro e na faixa de 95 a 107% para manganês. O método proposto foi aplicado para a determinação de ferro e manganês em seis amostras de vinho tinto. As concentrações obtidas variaram na faixa de 1,58 a 4,45 µg mL-1 para ferro e na faixa de 1,30 a 1,91 µg mL-1 para manganês. / Salvador

No description available.

A emissão de uma grande diversidade de substâncias através dos efluentes industriais gasosos, líquidos ou sólidos acarreta que uma gama de compostos seja introduzida no ambiente atmosférico e aquático de meios urbanos. A exposição a substâncias genotóxicas no ambiente oferece freqüentemente um grande risco à saúde humana. Com essa preocupação, o presente trabalho avaliou a exposição das pessoas à qualidade do ar atmosférico e à da água para abastecimento público de duas cidades urbanas do Rio Grande do Sul (Brasil), que recebem diferentes contribuições antrópicas (cidades-alvo), comparando-as com uma cidade menos impactada - cidade referência. Os extratos orgânicos da água tratada para abastecimento público e das amostras de ar foram testados quanto a mutagenicidade através do ensaio Salmonella/microssoma (linhagens TA98 e TA100 para água e ar, com e sem fração de metabolização e, ainda para ar, YG1021 e YG1024) - marcador de mutagenicidade. As amostras de ar ainda foram analisadas por HPLC para a caracterização de HPAs e algumas amostras também por HRGC-HRMS para a composição dos PCDD/Fs. Para o biomonitoramento humano foram avaliados através do ensaio do cometa e do micronúcleo (MN), em linfócitos e células da mucosa bucal, respectivamente, as pessoas que viviam nas três cidades - biomarcador de efeito. Análises de polimorfismos genéticos (CYP1A1, GSTM1 e GSTT1) foram utilizados como biomarcadores de susceptibilidade. As duas cidades-alvo apresentaram resultados significativos quanto a mutagenicidade da água de abastecimento apresentando todos os resultados positivos, principalmente para mutação de substituição de pares de bases (TA100), indicando a presença de compostos como THMs e MX. Valores de PTS atmosféricos apresentaram-se em algumas amostragens acima dos limites da legislação brasileira (CONAMA, 1990). Os HPAs encontrados em maior quantidade foram indeno(1,2,3-c,d)pireno e benzo(ghi)perileno, sendo que em uma das amostras a análise dos PCDD/Fs, mostrou valores que superaram em dez vezes a outra amostra analisada. As duas cidades alvo apresentaram altas respostas mutagênicas nas amostras de ar tanto por mutágenos de ação direta, como indireta e também altas concentrações de nitro-HPAs. Estes resultados sinalizaram para a necessidade de uma revisão da legislação para material particulado atmosférico, já que dentro dos atuais parâmetros, grande quantidade de compostos mutagênicos foram encontrados. Para os indivíduos estudados quanto aos biomarcadores de efeito, tanto os linfócitos analisados pelo ensaio do cometa quanto às células da mucosa bucal pelo ensaio do MN não apresentaram resultados significativos, sendo que apenas uma cidade alvo apresentou quanto ao ensaio do cometa. Como a maioria dos indivíduos CYP1A1, GSTM1 e GSTT1 apresentaram genótipos prevalentes, pode estar ocorrendo uma eficiência no sistema de detoxificação garantidos pela presença desses genótipos. Este trabalho mostrou a importância de estudos ambientais que relacionem marcadores de mutagenicidade com biomarcadores de efeito e de susceptibilidade, para que haja uma maior compreensão dos efeitos da exposição humana diária à agentes genotóxicos ambientais. / The emission of a great substances amount through gaseous, liquid and solid industrial effluents have been introduced many kinds of chemical compounds in aquatic and atmospheric environments. The environmental exposure to genotoxic substances often brings great risk to human health. Therefore, the aim of this work was make an avaliation of people exposition to atmospheric air and water supply quality in two urban cities in Rio Grande do Sul State (Brazil) which were under influence of different anthropogenic sources (target cities), compared to a less intense influenced urban city (reference city). The organic extracts from supply water and airborne samples were tested to mutagenicity using the Salmonella/microsome assay (TA98 and TA100 strains for water and airborne samples, with and without metabolization fraction, and also, YG1021 and YG1024 strains for airborne) - mutagenicity marker. Moreover, the airborne samples were analysed by HPLC to PAHs composition and by HRGC-HRMS to PCDD/Fs composition. Human biomonitoring was evaluated by samples of lymphocytes and bucal mucosa cells from individuals living in this three cities using the comet and the micronuclei (MN) assays, respectively - effect biomarkers. Analysis of gene polymorphisms (CYP1A1, GSTM1 and GSTT1) was taken as susceptibility biomarkers. Both target cities showed significative results for the water mutagenicity with mutagenic responses for all samples, mainly to base-pair substitution mutation (TA100 strain), denoting the presence of THMs and MX compounds. The TSP concentrations were above the Brazilian Legislation and World Health Organization regulation limits few times. The PAHs detected in greater amout were indeno(1,2,3-c,d)pyrene and benzo(ghi)perylene and one of the samples overcame ten times the values of PCDD/Fs compared to the other analysed. The two target cities showed high mutagenicity response in all airborne samples, both by direct and indirect mutagens, besides high concentrations of nitro-PHAs. Actually, these results indicate a law revision necessity, because great amount of mutagenic compounds were assessed in smaller concentration that those present in current legal parameters. The analysed subjects for effect biomarkers, both limphocytes tested by comet assay and buccal mucosa cells tested by MN, did not show significant results, only one city show increased primary DNA damage detected through comet assay. As the majority of subjects CYP1A1, GSTM1 e GSTT1 showed prevalent genotype, it maybe occuring an efficient system detoxification warranted by these genotypes presence. This work has shown the importance of environmental studies that relate mutagenicity markers with effect and susceptibility biomarkers, thus a greater understanding about environmental genotoxic agents, which people are exposed daily, will be done carefully.