Orientador: Joaquim Gonçalves Machado Neto / Banca: Julio Vicente Lombardi / Banca: Robinson Antonio Pitelli / Resumo: O inseticida diflubenzuron (DFB), comercializado como Dimilin®, é empregado em pisciculturas no tratamento de ecotoparasitoses em peixes. Este composto inibe a síntese de quitina, componente do exoesqueleto dos parasitas. A utilização deste inseticida se deve à sua baixa toxicidade aos peixes e eficácia no controle dos ectoparasitas. Porém, no ambiente aquático o DFB pode ser tóxico à espécies sensíveis e não-alvos, a concentração empregada no tratamento das ectoparasitoses é de 2 mg.L-1. Os objetivos deste estudo foram avaliar a toxicidade do DFB para as espécies de Daphnia magna, Poecilia reticulata e Lemna minor, classificar o produto quanto à sua toxicidade e risco ambiental e avaliar o efeito do sedimento na biodisponibilidade do DFB na água. Os organismos-teste foram submetidos a concentrações crescentes do inseticida em salas climatizadas do Laboratório de Ecotoxicologia da FCAV-UNESP. Os testes com D. magna foram realizados em volume de 10 mL a 20° C e cinco organismos neonatos por concentração, durante 48 horas na presença e ausência de sedimento. Os peixes (P. reticulata) foram expostos às concentrações do DFB por 96 horas em testes na presença e ausência de sedimento. O volume final foi de 3000 mL e cinco animais por concentração à 25° C. As plantas de L. minor foram expostas ao DFB por sete dias na presença e ausência de sedimento. O volume final foi de 100 mL e 12 frondes por concentração à 24° C. Os testes foram realizados com três réplicas incluindo o controle. As CE50-48h calculadas para D. magna foram de 0,56 μg.L-1 e 1,51 μg.L-1 na ausência e presença de sedimento respectivamente; as CL50-96h para P. reticulata foram 152,00 mg.L-1 e 277,83 mg.L-1 na ausência e presença de sedimento respectivamente; e as CE50-7dias para L. minor foram 459,50 mg.L-1 e 698,25 mg.L-1 na ausência e presença de sedimento respectivamente...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The insecticide diflubenzuron (DFB), marketed as Dimilin®, is used in fish farms to treat ectoparasites in fishes. This compound inhibits the chitin synthesis, exoskeleton component of the parasites. The use of this insecticide is due to its low toxicity for fish and effectiveness in the control of ectoparasites. However, the DFB in the aquatic environmental can be toxic to sensitive species and non-targed, the concentration used in the treatment of ectoparasites is 2 mg.L-1. The aims of this study were to evaluate the toxicity of the DFB for the species of Daphnia magna, Poecilia reticulata and Lemna minor, classify the product as to their toxicity and environmental risk and evaluate the effect of sediment on the bioavailability of the DFB in the water. The organisms-test were submitted to increasing concentrations of insecticide in air conditioned rooms of the Laboratory of Ecotoxicology FCAV-UNESP. Tests with D. magna were performed in volume of 10 mL at 20° C and five organisms neonates (6 and 24 hours of age) in each concentration, for 48 hours in the presence and absence of sediment. Fishes (P. reticulata) were exposed to concentrations of the DFB for 96 hours in tests in the presence and absence of sediment. The final volume was 3000 mL and five animals per concentration to 25° C. The plants of L. minor were exposed to the DFB for seven days in the presence and absence of sediment. The final volume was 100 mL and 12 fronds by concentration to 24° C. The tests were performed with three repetitions incluing the control. The EC50-48h estimeds for D. magna were 0.56 and 1.51 μg.L-1 in the absence and presence of sediment respectively; the LC50-96h for P. reticulata were 152.00 mg.L-1 and 277.83 mg.L-1 in the absence and presence of sediment respectively; and the EC50-7dias to L. minor were 459.50 mg.L-1 and 698.25 mg.L-1 in the absence and presence of sediment respectively...(Complete abstract, click electronic access below) / Mestre

Persistent organochlorines such as chlordecone (CD), DDT, and DDT degradation products bioaccumulate in fish and potentially impair reproduction or development via estrogenic actions. We evaluated the estrogenicity of CD, o,p'-DDT, o,p'-DDE, and p,p'-DDE injuvenile rainbow trout by assessing their potential to induce vitellogenesis; estrogen-regulated hepatic synthesis of the yolk-protein precursor, vitellogenin (Vg). In order to compare the sensitivities of various markers of estrogen stimulation, trout were injected with 17β-estradiol (0-10 mg kg-1) on days 0 and 3 and were sampled on days 3-12. Estradiol (5 mg kg-1) increased plasma Vg (2400%; 640 μg l-1), liver somatic index (200%) and hepatic cytosolic estrogen binding site levels (EBS, 300%) on day 6. These results suggested plasma Vg was the most sensitive marker of estrogen exposure. Chronic dietary exposure to CD (0.4 mg kg-1 day-1, 33 weeks) elevated plasma Vg (0.9 μg l-1), but not hepatic EBS concentrations, and resulted in relatively high hepatic CD concentrations (16 μg g-1). The in vivo estrogenicity of DDT was examined by injecting trout at 14 day intervals with single or triplicate doses of o,p'-DDT, o,p'-DDE or p,p'-DDE (0, 5, 15 or 30 mg kg-1) and monitoring vitellogenesis 14 days after the final injection. Plasma Vg and hepatic EBS concentrations were significantly elevated by o,p'-DDT and o,p'-DDE (total dose 45 and 90 mg kg-1; 23-24 μg Vg l-1) but not p,p'-DDE. Target organ doses were estimated by conducting a disposition study in which trout were injected with three doses of 14C]p,p'-DDE (30 mg kg-1), at 14 day intervals. Hepatic [14C]p,p'-DDE equivalent concentrations, 14 days after the final injection, averaged 14 μg g-1 Additionally, we evaluated the relative affinity of CD and DDT or DDE for trout hepatic EBS utilizing in vitro competitive binding assays. CD had relatively low affinity (1000-fold less than moxestrol, a synthetic estradiol) for trout hepatic EBS. o,p'-DDT and o,p'-DDE, but not p,p'-DEE also exhibited low EBS affinity (approximately 156000-fold less than moxestrol). Collectively, these results indicated that CD, o,p'-DDT and o,p'-DDE were weakly estrogenic in juvenile trout.

The role of intrinsic hydrodynamic instability of the premixed flame (known as Landau-Darrieus instability) in various flame phenomena is studied by means of direct numerical simulations of the complete system of hydrodynamic equations. Rigorous study of flame dynamics and effect of Landau-Darrieus instability is essential for all premixed combustion problems where multidimensional effects cannot be disregarded. The present thesis consists of three parts. The first part deals with the fundamental problem of curved stationary flames propagation in tubes of different widths. It is shown that only simple "single-hump" slanted stationary flames are possible in wide tubes, and "multi-hump" flames in a laminar flow are possible in wide tubes only as a non-stationary mode of flame propagation. The stability limits of curved stationary flames in wider tubes are obtained, together with the dependence of the velocity of the stationary flame on the tube width. The flame dynamics in wider tubes is shown to be governed by a large-scale stability mechanism resulting in a highly slanted flame front. The second part of the thesis is dedicated to studies of acceleration and fractal structure of outward freely propagating flames. It is shown that in direct numerical simulation the development of Landau-Darrieus instability results in the formation of fractal-like flame front structure. The fractal excess for radially expanding flames in cylindrical geometry is evaluated. Two-dimensional simulation of radially expanding flames in cylindrical geometry displays a radial growth with 1.25 power law temporal behavior after some transient time. It is shown that the fractal excess for 2D geometry obtained in the numerical simulation is in good agreement with theoretical predictions. The difference in fractal dimension between 2D cylidrical and three-dimensional spherical radially expanding flames is outlined. Extrapolation of the obtained results for the case of spherical expanding flames gives a radial growth power law that is consistent with temporal behavior obtained in the survey of experimental data. The last part of the thesis concerns the role of Landau-Darrieus instability in the transition from deflagration to detonation. It is found that in sufficiently wide channels Landau-Darrieus instability may invoke nucleation of hot spots within the folds of the developing wrinkled flame, triggering an abrupt transition from deflagrative to detonative combustion. It is found that the mechanism of the transition is the temperature increase due to the influx of heat from the folded reaction zone, followed by autoignition. The transition occurs when the pressure elevation at the accelerating reaction front becomes high enough to produce a shock capable of supporting detonation. / QC 20101119

Obesity is a worldwide problem affecting both children and adults. Genetic, physiological, environmental, psychological, social and economic factors interact in varying degrees, influencing body weight and fat distribution and the progress of obesity. Moreover, some anthropogenic chemicals have proven to be endocrine disrupting chemicals (EDCs) with the potential to interfere with different actions of hormones in the body. EDCs may thereby disrupt homeostasis, modifying developmental, behavioral and immune functions in humans and animals, and also promoting adiposity. Because hormones generally act at low concentrations, small changes in the endocrine system may lead to extensive effects. Based on data from experimental and epidemiological studies this thesis elucidates the relationship between a large number of environmental contaminants and obesity. The experimental studies demonstrated that fructose supplementation in the drinking water resulted in unfavorable metabolic alterations such as a higher liver somatic index (LSI), an increase in plasma triglycerides and increased plasma levels of apo A-I. Fructose in combination with exposure to bisphenol A (BPA) increased liver fat content and plasma levels of apo A-I in juvenile female Fischer 344 rats. The experimental studies also showed that the retro-peritoneal fat, which in rats is a distinct fat depot easy to distinguish and dissect, correlated well with the measurements of total fat mass analyzed with MRI, and could therefore be used as a substitute for total fat mass in rats. The epidemiological studies showed that circulating levels of persistent organic pollutants (POPs) were related to fat mass measured by DXA. OCDD, HCB, TNC, DDE and the less chlorinated PCBs were positively related to fat mass, while the more highly chlorinated PCBs showed a negative association. Further, circulating levels of BPA were positively associated with levels of the hormones adiponectin and leptin, but negatively related with ghrelin, hormones which are involved in the regulation of hunger and satiety. However, serum BPA levels were not related to measures of fat mass in the elderly individuals in the PIVUS cohort. This thesis concludes that environmental contaminants such as BPA and POPs most likely are contributors, along with genetic, social and behavioral factors, to the development of obesity.

Delayed auditory feedback (DAF) is known to produce speech disruptions in fluent speakers. The present study examined the relationship between individuals' susceptibility to DAF and their auditory processing skills. Forty participants (20 males and 20 females) read and produced monologue at no delay and 3 different delay levels of 100, 200, and 400 ms. Auditory processing skills were evaluated using dichotic digits test (DDT) and staggered spondaic word (SSW) test. Males produced significantly more Stuttering-Like Disfluencies (SLDs) under DAF than females. Significantly more SLDs were observed during conversation compared to reading. Overall, there was significant correlation between the frequency of SLDs and auditory performance on SSW test. Females scored significantly better on both SSW test and DDT compared to males. Scores on attention regulation questionnaire were not significantly different between genders. Fewer SLDs observed in females under DAF could be attributed to their superior control of auditory processing resources compared to males.

The necessity of cost effective, environmentally friendly technology has become increasingly important to remediate persistent organic pollutants in the environment. The emerging greener ultrasound technology has the potential to serve the remediation industry. In this study, the use of low power, high frequency (HF) ultrasound (1.6 MHz, 145 W/L) has been shown to effectively remediate DDT (90% of 8 mg/L) in water and sand slurries. Addition of iron powder accelerated DDT degradation in the sand slurry under ultrasonication. The potential of HF ultrasound (1.6 MHz, 160 W/L) in degradation of the non-volatile, polar model compound methylene blue (MB) was studied in MB spiked demineralised water and wastewater. A 70 % of 0.4 mg/L of MB was degraded in demineralised water whereas only 54% of MB degraded in MB spiked wastewater. There was a decrease in MB degradation rate with an increase in MB concentration. High power, low frequency (LF) ultrasound (20 kHz, 932 W/L) was used to desorb 400 mg/L of DDT added to three different natural soil slurries at 5, 10, 15 and 20 wt. % each. Each soil slurry was prepared in 0.1% v/v SDS surfactant solution, soaked for 30 min. and heated for another 30 min. at 40 oC before sonication. For the neutral pH soil slurry with higher dissolved organic carbon, the desorption efficiency achieved was over 80% in 30 s sonication. Alkaline soil with higher surface area than neutral soil indicated 60% desorption efficiency while the acidic soil, with the highest surface area and a higher amount of non-soluble organic matter, yielded 30% desorption efficiency under similar desorption conditions. Coconut fibre, used to biosorb the desorbed DDT in the decanted solution, was found to have over 25 g/kg of biosorption capacity for DDT. The surfactant SDS and associated DDT were completely separated from decanted liquid of the desorbed slurry with alum using adsorptive micellar flocculation in 60 min. settling. Acidic pH and molar concentration ratio of Al3+/SDS = 0.5 was used to completely remove the DDT. Using 20 kHz, 1125 W/L of sonication in an 80 mL reactor with air saturated 50 mg/L DDT at 20oC, the DDT removal efficiency achieved was 80% in 20 min. With zero valent iron addition, DDT removal efficiency in 15 min. is 100% with 15 and 22 mg/L of initial DDT concentrations. The settled DDT slurrywas remediated using 20 kHz at 240 W/L achieving DDT removal efficiency of 87% in 15 min. Also LF ultrasound was found to be effective in remediating chloroform (8 mg/L in 60 min) from spiked demineralised water and contaminated groundwater in both batch (120 W/L) and flow cell (6000 W/L) modes. Modeling and simulation of the ultrasonic reactor under 20 kHz ultrasonication was performed for various shape reactors using commercially available software. For almost all reactors, the highest ultrasonic intensity was observed near the transducer???s vibrating area. It was found that the highest acoustic pressure distribution, which is critical to the performance of the reactor, occurred in the conical reactor and flow cell configuration. / Thesis (PhD)--University of South Australia, 2010

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.

Pulsed Detonation Engines (PDEs) have the potential to revolutionize fight by better utilizing the chemical energy content of reactive fuel/air mixtures over conventional combustion processes. Combustion by a super-sonic detonation wave results in a significant increase in pressure in addition to an increase in temperature. In order to harness this pressure increase and achieve a high power density, it is desirable to operate PDEs at high frequency. The process of detonation initiation impacts operating frequency by dictating the length of the chamber and contributing to the overall cycle time. Therefore a key challenge in the development of a practical PDEs is the requirement to rapidly initiate a detonation in hydrocarbon-air mixtures. This thesis evaluates the influence of spark energy and airflow velocity on this challenging initiation process. The influence of spark energy, number of sparks and airflow velocity on Deflagration-to-Detonation Transition (DDT) was studied during cyclic operation of a small-scale PDE at the General Electric Global Research Center. Experiments were conducted in a 50 mm square transitioning to cylindrical channel PDE with optical access operating with stoichiometric ethylene-air mixture. Total spark energy was varied from 250 mJ to 4 J and was distributed between one and four spark plugs located in the same axial location. Initial flame acceleration was imaged using high-speed shadowgraph and was characterized by the time to reach 20 cm from the spark plug. Measurements of detonation wave velocity and emergence time, the time it takes the detonation wave to exit the tube, was measured using dynamic pressure transducers and ionization probes. It was found that the flame front spread was faster at higher spark energies and with more spark locations. Initial flame acceleration was 16% faster for the 4-spark, 4 J case when compared to the baseline 1-spark, 1 J case. When looking at the effect of airflow on the influence of spark energy, it was found that airflow had a larger effect on emergence time at high energies, versus energies less than 1 J. Finally, for a selected case of 0.25 J spark energy and 4 sparks, the velocity of the fuel-air mixture during fill was found to have a varying influence on detonation initiation and emergence time.

Past and present uses of DDT and pyrethroids have led to their incorporation into humans, mainly through the food chain and sometimes by direct exposure. The present work focuses on establishing the levels of DDT, its analogous compounds (DDE and DDD), and pyrethroids in humans and the human environment in Manhiça, a rural area where they have been used as insecticides for indoor residual spraying (IRS) and insecticide treated nets (ITN) in malaria control programs. Thatch samples from human dwellings, breast milk from pregnant women and cord blood from newborns were analyzed for assessment of the concentration levels of these compounds. The results showed that DDT and its analogues were already present in humans and dwellings before reintroduction of this insecticide for IRS. As consequence of these applications DDT concentrations increased significantly. The higher proportion of 4,4’-DDT than 4,4’-DDE evidenced that the observed amounts were due to recent applications of this insecticide. Concerning pyrethroids, their presence has been identified in both breast milk and human dwellings showing that both agricultural applications and use for ITN may be responsible for their occurrence in humans and human environments of Manhiça. / L’ús en el passat i en temps actuals del DDT i piretroides ha donat lloc a la seva incorporació en els humans, principalment mitjançant la cadena tròfica i a vegades per exposició directa. Aquest treball té com objectiu establir els nivells de DDT i els seus compostos anàlegs (DDE i DDD), i piretroides en humans i l’ambient humà a Manhiça, una àrea rural on aquests s’han utilitzat com insecticides per aplicació interna (indoor residual spraying, IRS) i tractament de xarxes de protección (insecticide treated nets, ITN) en programes de control de la malària. Per a esbrinar els nivells de concentració d’aquests compostos s’analitzaren mostres de palla de cabanes, de llet materna i de sang de cordó de nou nats. Els resultats mostraren que el DDT i els seus compostos anàlegs ja eren presents en humans i cabanes abans de la reintroducció d’aquest insecticida per IRS. L’ús del DDT en aquest programa féu augmentar considerablement les concentracions d’aquest insecticida. La major proporció de 4,4’-DDT que 4,4’-DDE posà de manifest que les quantitats observades corresponien a aplicacions recents d’aquest insecticida. Respecte als piretroides, s’han trobat en mostres de llet materna i cabanes tot mostrant que tant les aplicacions agrícoles com el seu ús en ITN poder esser la causa de la seva presència en els humans i els ambients humans de Manhiça.

The necessity of cost effective, environmentally friendly technology has become increasingly important to remediate persistent organic pollutants in the environment. The emerging greener ultrasound technology has the potential to serve the remediation industry. In this study, the use of low power, high frequency (HF) ultrasound (1.6 MHz, 145 W/L) has been shown to effectively remediate DDT (90% of 8 mg/L) in water and sand slurries. Addition of iron powder accelerated DDT degradation in the sand slurry under ultrasonication. The potential of HF ultrasound (1.6 MHz, 160 W/L) in degradation of the non-volatile, polar model compound methylene blue (MB) was studied in MB spiked demineralised water and wastewater. A 70 % of 0.4 mg/L of MB was degraded in demineralised water whereas only 54% of MB degraded in MB spiked wastewater. There was a decrease in MB degradation rate with an increase in MB concentration. High power, low frequency (LF) ultrasound (20 kHz, 932 W/L) was used to desorb 400 mg/L of DDT added to three different natural soil slurries at 5, 10, 15 and 20 wt. % each. Each soil slurry was prepared in 0.1% v/v SDS surfactant solution, soaked for 30 min. and heated for another 30 min. at 40 oC before sonication. For the neutral pH soil slurry with higher dissolved organic carbon, the desorption efficiency achieved was over 80% in 30 s sonication. Alkaline soil with higher surface area than neutral soil indicated 60% desorption efficiency while the acidic soil, with the highest surface area and a higher amount of non-soluble organic matter, yielded 30% desorption efficiency under similar desorption conditions. Coconut fibre, used to biosorb the desorbed DDT in the decanted solution, was found to have over 25 g/kg of biosorption capacity for DDT. The surfactant SDS and associated DDT were completely separated from decanted liquid of the desorbed slurry with alum using adsorptive micellar flocculation in 60 min. settling. Acidic pH and molar concentration ratio of Al3+/SDS = 0.5 was used to completely remove the DDT. Using 20 kHz, 1125 W/L of sonication in an 80 mL reactor with air saturated 50 mg/L DDT at 20oC, the DDT removal efficiency achieved was 80% in 20 min. With zero valent iron addition, DDT removal efficiency in 15 min. is 100% with 15 and 22 mg/L of initial DDT concentrations. The settled DDT slurrywas remediated using 20 kHz at 240 W/L achieving DDT removal efficiency of 87% in 15 min. Also LF ultrasound was found to be effective in remediating chloroform (8 mg/L in 60 min) from spiked demineralised water and contaminated groundwater in both batch (120 W/L) and flow cell (6000 W/L) modes. Modeling and simulation of the ultrasonic reactor under 20 kHz ultrasonication was performed for various shape reactors using commercially available software. For almost all reactors, the highest ultrasonic intensity was observed near the transducer???s vibrating area. It was found that the highest acoustic pressure distribution, which is critical to the performance of the reactor, occurred in the conical reactor and flow cell configuration. / Thesis (PhD)--University of South Australia, 2010