PhD. (Department of Biotechnology, Faculty of Applied and Computer Sciences), Vaal University of Technology. / South Africa utilises more antiretroviral (ARV) compounds per capita than any other nation in the fight against Human Immune Deficiency Virus (HIV) or acquired immunodeficiency syndrome (AIDS). Considering the main entrance pathways of antiviral drugs into the urban water cycle, excretions via urine or faeces from treated individuals play a dominant role. Due to the limited efficiency of conventional biological treatment (activated sludge), ARVs were detected in South African wastewater treatment plant effluents and surface waters. This poses a threat to aquatic environments due to the toxicity of ARVs and can be a potential contributor to ARV resistance due to persistent low level ARV exposure in the general population. This study investigated the efficacy of a moving bed biofilm reactor (MBBR) for ctybtri8nthe elimination of five ARV compounds i.e., tenofovir, emtricitabine, nevirapine, ritonavir and efavirenz from synthetic wastewater. Furthermore, the study also looked at the shift in microbial community compositions of biofilms in the MBBR due to exposure to the ARV compounds. Lastly, the ecotoxicity of the MBBR’s influent and effluent along with the actual ARV compounds were examined. The capacity of ARV degradation by the MBBR was investigated by spiking synthetic wastewater influent with 10 μg/L of five ARV compounds. Actual removal during treatment was assessed by sampling the inlets and outlets of the reactor. A targeted solid phase extraction method with Ultra High Pressure Liquid Chromatography coupled to quadrupole time of flight mass spectrometry (LC-MS/MS) was used to quantify the five ARV compounds. Microbial diversity (alpha-diversity) of seeded sludge from a full-scale municipal WWTP and biofilm samples from a laboratory scale MBBR system during pre- and post-introduction of ARV compounds was investigated by Illumina sequencing of the 16S rRNA gene. Ecological toxicity of the MBBR’s influent and effluent along with the five ARV compounds was determined using the Vibrio fischeri, Daphnia magna and Selenastrum capricornutum toxicity test kits and measured as EC50. After MBBR treatment; Nevirapine, Tenofovir, Efavirenz, Ritonavir and Emtricitabine all showed marked reduction in concentration between the influent and effluent of the MBBR. On average, the percentage removed for Nevirapine, Tenofovir, Efavirenz, Ritonavir and Emtricitabine was 62.31%, 74.18%, 93.62%, 94.18% and 94.87% respectively. Microbial diversity results demonstrated that the introduction of antiretroviral drugs affects the bacterial community composition and diversity considerably. For instance, Nitrosomonas, Nitrospira and Alicycliphilus were found to be higher in post introduction of ARV compounds biofilm samples than in biofilm samples before the introduction of ARV compounds. The EC50 for Tenofovir, Emtricitabine, Nevirapine, Ritonavir and Efavirenz were 82.5, 41.7, 39.3, 60.3 and 0.21 mg/L respectively for S. capricornutum; 81.3, 50.7, 49, 87.1 and 0.43 mg/L respectively for D. magna; and 73.5, 55.1, 41.3, 83.6 and 0.55 mg/L respectively for V. fischeri. The EC50 of the influent and effluent were found to be above 100% concentration, therefore they could not be specifically determined. The ecotoxicity results show that ARV compounds are potentially toxic to the environment, with efavirenz being more toxic than the other four ARV compounds tested. Since there were no toxic effects observed from the effluent, it can be assumed that mineralisation has occurred, or the transformation products are of less or equal toxicity to the influent (because the influent did not show any toxic effects to the model organisms tested).

Ph. D. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Driven by the need of sustainably sourced catalysts and the use of reaction systems that generate environmentally benign by-products, the present study aimed to deposit stable, dispersed palladium (Pd) nanoparticles on the modified surfaces of granular macadamia nutshell (MNS) biomass for catalytic reduction of hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)]. Through wet impregnation with Pd(II) ions and subsequent hydrazine-mediated reduction to Pd(0), Pd nanoparticles were embedded in a scaffold of polyethyleneimine grafted on bleached MNS previously coated with a chemically bound layer of polyglycidyl methacrylate. Visualization and imagery from scanning electron microscopy showed the formation of different layers of the polymeric coating and dispersed palladium resulting from surface modification and palladium nanoparticle synthesis, respectively. X-ray diffraction, energy-dispersive X-ray spectroscopic analysis confirmed the formation of Pd on the modified MNS surface. An estimate of 5.0 nm for crystallite size was calculated by application of the Scherrer equation. The composite material, denoted Pd@PEI-MNS, exhibited catalytic activity in formic acid-mediated Cr(VI) reduction. Through a one-factor-at-a-time experimental design, the activity of the Pd@PEI-MNS was illustrated to be dependent on solution pH; initial Cr(VI) concentration, initial formic acid concentration, and presence of competing anions; Pd@PEI-MNS dose; and temperature. Subsequent modeling of the Cr(VI) removal process by response surface methodology revealed that the most influential factor was Pd@PEI-MNS dose followed by temperature and formic acid concentration. The influence of initial Cr(VI) concentration, was surpassed by the dose-temperature and dose-formic acid concentration interactive effects. Elucidation of the Cr(VI) removal mechanism by XPS and FTIR demonstrated the active participation of surface -CH2OH functional groups, the bulk of which originated from the reduction of esters of the grafted ligands. Replacement of formic acid to carbon dioxide, the -CH2OH groups were converted to -COO- groups.

Two plant species including Polygonum hydropiper L. and Hymenachne acutigluma (Steud.) Gilliland were investigated in their resistance to lead (Pb) and cadmium (Cd) pollution in the soil. Lead-contaminated soil samples were collected from the lead recycling village Dong Mai, Chi Dao commune, Van Lam district, Hung Yen province, Vietnam that had Pb level up to 192,185 mg.kg-1, dry weight (DW). Cadmium-contaminated soil samples were due to supplement of CdCl2.21/2H2O to alluvial soil. Results showed that both species were highly resistant to Pb, however P.hydropiper was better. Similarly, the Cd resistance was higher for P.hydropiper than for H.acutigluma. No morpho-abnormalities of P.hydropiper regarding the impact of lead were recorded, whereas for H.acutigluma, the young leaves had white colour after two months of planting in soil containing lead levels of 192,185 mg.kg-1. The response of both species with Cd in soils included yellowing leaves, withering branches and even dying after 5-15 days exposed to Cd. Lead contents accumulated in above-ground parts of both plants were up to 4,650 and 3,161 mg.kg-1, DW, corresponding to P.hydropiper and H.acutigluma. From the research results on lead resistance and accumulation of two plant species studied, it is suggested that the two species are lead hyperaccumulators can be used for phytoremediation technology to clean contaminated soil. / Hai loài thực vật gồm nghể răm Polygonum hydropiper L. và bấc nhọn Hymenachne acutigluma (Steud.) Gilliland được nghiên cứu về khả năng chống chịu ô nhiễm chì (Pb) và cadmi (Cd) trong đất. Mẫu đất ô nhiễm chì được thu từ làng nghề tái chế chì Đông Mai, xã Chỉ Đạo, huyện Văn Lâm, tỉnh Hưng Yên, Việt Nam có hàm lượng chì lên đến 192.185 mg.kg-1, tính theo trọng lượng khô (DW). Mẫu đất ô nhiễm Cd là do được bổ sung CdCl2.21/2H2O vào đất phù sa. Kết quả cho thấy cả hai loài đều có sức chống chịu chì rất cao, tuy nhiên nghể răm có khả năng tốt hơn. Tương tự như vậy, sức chống chịu Cd của nghể răm cũng cao hơn của bấc nhọn. Không có dấu hiệu bất thường nào của nghể răm đối với tác động của chì được ghi nhận, trong khi ở bấc nhọn thì lá non có màu trắng sau hai tháng trồng trên đất có hàm lượng chì 192.185 mg.kg-1. Phản ứng của cả hai loài thực vật với Cd trong đất gồm có hiện tượng vàng lá, héo ngọn và thậm chí chết sau 5-15 ngày phơi nhiễm với Cd. Hàm lượng chì được tích lũy cao trong phần trên mặt đất của cả hai loài thực vật lên tới 4.650 và 3.161 mg.kg-1, DW, tương ứng cho loài P.hydropiper và H.acutigluma. Từ kết quả nghiên cứu về khả năng chống chịu và tích lũy chì của hai loài thực vật nghiên cứu, có thể đề xuất đây là hai loài siêu tích lũy chì có thể sử dụng trong công nghệ làm sạch đất ô nhiễm.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-09-03T17:30:48Z No. of bitstreams: 1 MORGANA FABÍOLA CUNHA SILVA CANUTO - TESE PPGEP 2012..pdf: 1607652 bytes, checksum: 0c3a5a7e86e448696445e64563fdd07d (MD5) / Made available in DSpace on 2018-09-03T17:30:48Z (GMT). No. of bitstreams: 1 MORGANA FABÍOLA CUNHA SILVA CANUTO - TESE PPGEP 2012..pdf: 1607652 bytes, checksum: 0c3a5a7e86e448696445e64563fdd07d (MD5) Previous issue date: 2012-10 / CNPq / A degradação dos ambientes aquáticos por metais pesados está relacionado ao aumento desenfreado do setor industrial. A biossorção é uma alternativa eficiente e de baixo custo para o tratamento dos efluentes contaminados por metais pesados que são lançados no meio ambiente por parte das indústrias, Uma alternativa para a remoção de metais pesados presentes em efluentes líquidos é o processo de adsorção em colunas de leito fixo utilizando a levedura Saccharomyces cerevisiae imobilizada com quitosana. Experimentos da cinética de biossorção foram realizados em tanque agitado utilizando os bioadsorventes, esferas de quitosana, levedura Saccharomyces cerevisiae livre e imobilizada com quitosana para remoção do íon Cd2+, enquanto que os experimentos do equilíbrio de adsorção e em coluna de leito fixo, realizados com a levedura imobilizada. Os modelos pseudo-segunda ordem e o de Michaelis Menten apresentaram um bom ajuste aos dados experimentais, enquanto para o estudo do equilíbrio o modelo de Langmuir foi o que melhor representou a isoterma de adsorção. As curvas de ruptura obtidas para concentrações do íon Cd2+ de até 20 mg.L-1 demonstraram que o leito estava longe de atingir a saturação, porém ao ampliar a faixa de concentração 40 – 90 mg.L-1, o leito ficou mais próximo da saturação, sendo verificado a viabilidade de se utilizar este bioadsorvente para o tratamento de efluentes que contenham Cd2+. A técnica de planejamento experimental foi utilizada para avaliar os efeitos das variáveis concentração do efluente sintético e vazão de operação sobre a quantidade adsorvida de Cd2+ e o percentual de remoção. O efeito da vazão de operação é o fator mais significativo seguido da concentração do íon Cd2+, para a variável resposta quantidade adsorvida de Cd2+, enquanto apenas a variável vazão de operação foi estatisticamente significativa sobre o percentual de remoção. Os modelos matemáticos, da Força Impulsora Linear e o de Thomas, descreveram satisfatoriamente o comportamento das curvas de ruptura. / The degration of aquatic ecosystems caused by metallic ions is related to the unbridled increase in industrial sector. Biosorption is an efficient and low cost alternative for the treatment of effluents contaminated by metallic ions, which are thrown by industries into the environment. An alternative in order to remove these ions into the liquid effluents is a process of biosorption in fixed bed columns using Saccharomyces cerevisiae yeast immobilized with Chitosan. Biosorption's kinetics experiments were conducted in agitated tanks using bioadsorbing, chitosan's spheres, free Saccharomyces cerevisiae yeast and immobilized with chitosan to remove Cd2+ ion, whereas the equilibrium experiments of biosorption and in a fixed bed column, were conducted with immobilized yeast. Both pseudo-second order and Michaelis Menten models prevented a good adjustment to the experimental data, whereas to the equilibrium study, Langmuir's model was the one which better represented the adsorption's isotherm. The rupture curves got by Cd2+ ion concentration of up to 20 mg.L-1 show that the bed was far from reaching saturation. Nevertheless, by extanding the concentrations of 40-90 mg.L-1, the bed got closer to saturation and being checked the viability of using this bioadsorvent to treating effluents which contains Cd2+. The experimental planning techinique was used to evaluate the effects of concentration variables from the sinthetic aqueous solution of Cd2+ in the entry of the bed and flow of operation over a quantity adsorbed and the removal percentage. The flow operation effect was the most significant factor being followed by the concentration for the response variable amount absorbed, whereas only the flow variable from operation was statiscally significant about removal percentage. Mathematical models of Linear Driving Force and Thomas' satisfactorily described the breakthrough curves behavior.

Ce travail présente un dispositif de surveillance épidémiologique novateur en santé environnementale fondée sur des évènements de santé déclarée, au plus près de la nature des plaintes exprimées par les populations : des symptômes et une dégradation de la qualité de vie. Ce dispositif est proposé à partir d’une réflexion conceptuelle reposant sur une revue de la littérature sur les théories psychométriques et le modèle transactionnel du stress et d’une application de terrain portant sur la population (n=1 495) riveraine du site industriel chimique de Salindres (Gard). Ces travaux permettent de vérifier les principales propriétés métriques d’indicateurs de santé déclarée mesurés, par les instruments MOS SF-36 et SCL-90-R, dans le cadre d’une population exposée à une pollution environnementale. Ils vérifient également l’adéquation et la sensibilité de ces indicateurs pour étudier les facteurs de risque environnementaux qui se réfèrent aux représentations cognitives des risques, comme la perception sensoriels des stimuli émis par les sites industriels. Ils montrent, en outre, que la disponibilité de références nationales portant sur la mesure de ces indicateurs leur confère un critère de qualité essentiel d’interprétation des résultats. Ces travaux apportent enfin des éléments d’appréciation de l’acceptabilité de la mesure des indicateurs de santé déclarée dans la population, des recommandations sur la communication pour la mise en œuvre d’un tel dispositif et des pistes de réflexion pour la gestion. / This work presents an innovative epidemiological surveillance system in environmental health based on self-reported health indicators, closer to the complaints of the local population leaving around a source of environmental pollution: symptoms and loss of the quality of life. This approach is built up from a conceptual framework based on the psychometric theory and the transactional model of stress. A field application of this approach was carried out the population neighboring (n=1 495) the chemical industrial area of Salindres, Gard. This study verifies that self-reported health indicators measured with MOS SF-36 and SCL-90-R can be used to study populations exposed to multifactorial environmental risks. This study confirms that these indicators are relevant and sensitive when applied to environmental risk factors referring to the cognitive representations of risks, such as the sensorial perception of stimuli emitted by the industries. This work shows, besides, that the availability of national references for these indicators confers interpretability to these indicators, an essential quality criterion. This work discusses qualitatively the acceptability of measuring indicators of self-reported health in the population, proposes recommendations on communication for the setting of that kind of approach, and opens up avenues on management orientations.

Dans ce travail de thèse, nous avons évalué les effets inflammatoires, comportementaux et cognitifs de l’exposition périnatale des souris à trois matrices alimentaires d’anguilles, reflétant 3 niveaux de pollution (faible, moyenne et haute), tout en considérant le sexe de la progéniture ainsi que les différentes phases d’âges. Les réponses inflammatoires ont été évaluées, aussi bien au niveau cérébral, y compris dans les cellules de la microglie, qu’au niveau périphérique, à 4 stades de vie distincts, et ce dès la naissance jusqu’à l’âge moyen. Chez les souriceaux, mâles et femelles, dont leurs génitrices ont consommé de l’anguille contaminée, durant la période gestationnelle et lactationnelle, vs les témoins dont leurs mères ont consommé uniquement la diète standard, nos résultats ont montré une neuro-inflammation précoce et prononcée, ainsi qu’une production accrue des marqueurs pro-inflammatoires par les cellules de la microglie durant la période néonatale et postnatale. Cette réponse pro-inflammatoire a été chronique puisqu’elle a été à nouveau détectée même à un âge avancé (âges adulte et moyen). Nos résultats mettraient en évidence l’activation et la polarisation des cellules de la microglie depuis la naissance, chez les animaux exposés, vers le phénotype M1, susceptible d’induire les effets neurotoxiques apparus beaucoup plus tard dans les stades de la vie. En effet, un comportement dépressif-like a été observé à l’âge adulte uniquement chez les mâles. Cette altération sexe dépendante du comportement de résignation a été attribuée à l’hyperactivation de l’axe de stress, l’axe hypothalamique pituitaire surrénalien, mise en évidence par une forte production de la corticostérone chez les mâles à l’âge adulte. Chez les femelles, nous avons mis en évidence le développement d’un comportement hyperactif dès l’âge adulte, et d’un déclin cognitif à l’âge moyen. Nos résultats suggèrent que le déficit de la mémoire de rétention des femelles d’âge moyen exposées périnatalement à des anguilles moyennement et hautement contaminées serait lié à la diminution significative de l’activation à la fois d’ERK ½ et du NF-κB ainsi qu’à la réduction significative du taux d’acétylcholine, détectées au niveau de l’hippocampe de ces souris. A partir de ces données et de celles obtenues par d’autres membres de notre équipe, il apparait de plus en plus pertinent de prendre en considération le risque du couplage des effets neuro-oxydatif et neuro-inflammatoire dans la genèse de nombreux troubles cognitifs et comportementaux surtout de manière tardive et irréversible. Cela pourrait également être à l’origine d’une fragilité et d’une imprégnation précoce de différentes populations cellulaires qui conduiraient tardivement à une dégénérescence précoce des cellules en particulier au niveau neuronal et glial. En conclusion, nos résultats suggèrent une programmation périnatale sexe-dépendante des troubles, mis en évidence aussi bien sur le plan comportemental que sur le plan cognitif chez les souris dont leurs mères ont consommé de l’anguille polluée, via des mécanismes inflammatoires. Cela laisse supposer un impact endocrino-dépendant dont il faudrait confirmer la réalité et les mécanismes / Several lines of evidence indicate that early-life inflammation may predispose to mental illness in later-life. In our study, we investigated the impact of perinatal exposure to polluted eels on the brain and microglia inflammation in a lifespan approach as well as on the resignation behavior, the locomotor activity and the cognitive performances in the later life of male and female offspring mice. The effects of maternal standard diet (laboratory food) were compared to the same diet enriched with low, intermediate, or highly polluted eels. Our results showed a chronic brain inflammation in male and female offspring mice compared to controls, as assessed at the birth, up weaning, adulthood and middle-age. Activated microglia produced pro-inflammatory markers across the lifespan of male as well as female exposed offspring. The plasmatic level of myeloperoxidase was found to be significantly higher in both adult and middle-aged males and females vs. control offspring. However, high corticosterone levels were only found in adult male offspring mice perinatally exposed to polluted eels, suggesting a sex-selective dysregulation of the adult hypothalamic- pituitary- adrenal (HPA) axis. Sex selective differences were also found in adulthood, with regard to the offspring resignation behavior. Indeed, depressive-like symptoms were only found in adult male mice perinatally exposed to polluted eels. On the middle- age, sexe selective effects were found with regard to memory and locomotor activity. Indeed, hyperactive phenotype was only detected in females. In addition, impaired long-term memory was only detected in middle-aged females, perinatally exposed to either intermediately or highly polluted eels. This deficit was related to decreases in ERK1/2 and p65 activation, and acetylcholine levels that were only detected in female hippocampus exposed to either intermediately or highly polluted eels. In conclusion, our results indicated that early-life inflammatory insults were the plausible causative factor that programmed the behavior impairments and cognitive deficit in the later-life of offspring, and suggested that sex played an important role in the determination of nature of the appeared alterations