Membrane desalination has become one of the most important desalination technologies used in the world. It provides high water quality for numerous applications and it demonstrates excellent desalination efficiency. One of the most troubling drawbacks of membrane desalination is membrane fouling. It decreases the performance of the membranes and increases the energy requirement. Two of the most important causes of fouling are microbes and organic matter. Hence, to maintain an optimized desalination performance, routine inspection of microbial and organic contents of water is crucial for desalination plants. In this study, water samples were obtained from different treatment points in an ultrafiltration (UF)/nanofiltration (NF) seawater desalination pilot plant. This was performed to better understand how the water quality changes along the desalination scheme. The effect of fouling control techniques, including Chemically Enhanced Backwash (CEB), Cleaning in Place (CIP), and the addition of a biocide (DBNPA) was studied. Different analytical tools were applied, including Bactiquant, Total Organic Carbon (TOC), Assimilable Organic Carbon (AOC), and Liquid Chromatography for Organic Carbon Detection (LC-OCD). Out results showed that UF did not decrease TOC but it was sufficient in removing up to 99.7% of bacteria. Nanofiltration, removed up to 95% of TOC. However, NF permeate had a high increase in AOC as compared to the raw seawater sample. The LC-OCD results suggested that this might be due to the increased low molecular weight neutrals which were the most common organic species in the NF permeate. The fouling control techniques showed various effects on the desalination efficiency. Daily CEB did not cause a reduction in TOC or bacteria but decreased AOC in the UF filtrate. The biocide addition resulted in an adequate membranes protection from fouling and it did not affect the investigated water parameters. When the dosing of biocide was stopped, the water quality parameters did not change, but the NF pressure drop increased rapidly, indicating fouling of this membrane. CIP did not show an impact on the organic and microbial contents of water, but it was efficient in restoring the operations back to acceptable pressure levels. These results indicated that the applied fouling protection techniques were beneficial in fouling control.

A novel core-shell silica based antimicrobial nanoparticle was synthesized. The Stöber silica shell has been engineered to accommodate copper. Synthesis of the core-shell Cu-silica nanoparticle (C-S CuSiNP) involves preparation of base-hydrolyzed Stöber silica “seed” particles first, followed by the acid-catalyzed seeded growth of the Cu-silica shell layer around the core. Scanning electron microscopy and transmission electron microscopy showed monodispersed, spherical shaped nanoparticles with smooth surface morphology. Characterization of particle size distribution in solution by the Dynamic Light Scattering (DLS) technique was fairly consistent with the electron microscopy results. Loading of Cu to nanoparticles was confirmed by the SEM-Energy Dispersive X-Ray Spectroscopy (EDS) and Atomic Absorption Spectroscopy (AAS). Antibacterial efficacy of C-S CuSiNP was evaluated against E.coli and B.subtilis using Cu hydroxide (“Insoluble” Cu compound) and copper sulfate as positive control and silica “seed” particles (without Cu loading) as negative control. Minimum Inhibitory Concentration (MIC) of C-S CuSiNP was evaluated by measuring the fluorescent intensity of resorufin to determine the decrease in viable cells with increase in copper concentration in C-S CuSiNP. The MIC value of C-S CuSiNP against both E.coli and B.subtilis was estimated to be 4.9 ppm. Bac-light fluorescence microscopy based assay was used to count relative population of the live and dead bacteria cells. Antibacterial study clearly shows that C-S CuSiNP is more effective than insoluble Cu hydroxide particles and copper sulfate at equivalent metallic Cu concentration, suggesting more soluble Cu in C-S CuSiNP material due to its coreshell design.

Copper (Cu) compounds are widely used as effective agricultural bactericides. Continuous use of these materials has led to Cu accumulation in soil over time. The United States Environmental Protection Agency (US EPA) is concerned about potential Cu contamination in the environment. Improving biocidal efficacy of Cu is an attractive alternative, allowing reduction of Cu amount per application. In this research, we focused on making watersoluble mixed-valence Copper/Silica composite nanogel (CuSiNG) material. The objective is to improve the efficacy of Cu by manipulating Cu valence states. It has been shown in the literature that Cu (0) and Cu (I) states are more potent that Cu (II) states in terms of their antimicrobial efficacy. It is hypothesized that mixed valence Cu will exhibit improved efficacy over Cu (II). A water-soluble mixed valence Cu/silica nanogel (MV-CuSiNG) composite has been synthesized and characterized. Structure, morphology, crystallinity and composition of the MV-CuSiNG material was characterized using High-Resolution Transmission Electron Microscopy (HRTEM), HRTEM Selected Area Electron Diffraction (SAED) and X-ray Photoelectron Spectroscopy (XPS). Amount of Cu loading in MV-CuSiNG composite material was estimated by Atomic Absorption Spectroscopy (AAS). To confirm presence of Cu (I) in the MV-CuSiNG material, Neocuproine (Nc, a Cu (I) specific chelator) assay was used. Antimicrobial efficacy of MVCuSiNG and CuSiNG was evaluated against X.alfalfae, B.subtilis and E.coli using Kocide® 3000 ("Insoluble Cu (II)" compound), Copper sulfate ("Soluble Cu (II)" compound) and Cuprous chloride (Copper (I) compound) as positive controls and silica "seed" particles (without Cu loading) as negative control. Antimicrobial studies included observing bacterial growth inhibition and determining the Minimum Inhibitory Concentration (MIC). Improved antimicrobial efficacy was observed in MV-CuSiNG when compared to CuSiNG and other controls. For the assessment of plant safety of MV-CuSiNG and CuSiNG materials, phytotoxicity studies were conducted using Vinca sp and Hamlin orange under environmental conditions. It was observed that MV-CuSiNG material was safe to plants at commercially used

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[pt] O crescimento microbiológico em águas de sistemas de resfriamento pode resultar na formação de biofilme, o qual pode causar problemas de biocorrosão, perdas de carga em tubulações, redução de taxa de transferência de calor e obstrução de fluxo. Os principais e tradicionais biocidas utilizados no controle microbiológico de águas de resfriamento são os compostos à base de cloro. Entretanto, nos últimos anos o ácido peracético tornou-se uma alternava aos compostos clorados, uma vez que este biocida deixa como resíduo apenas o acetato o qual é biodegradável e não forma subprodutos organoclorados. Este trabalho analisou a aplicação do ácido peracético comparando-o com o hipoclorito de sódio no controle microbiológico e na corrosividade de materiais, empregando uma árvore de teste em escala de laboratório. Foi investigada a taxa de corrosão dos materiais metálicos de aço carbono, cobre e aço inoxidável, além da efetividade na redução da contagem bacteriana. Os experimentos foram realizados em condições de fluxo turbulento, pH 8 e temperatura de 32 C empregando uma água de estudo real, carregada de matéria orgânica (DQO = 350 mg/L). As concentrações usadas de ácido peracético foram 0,75; 1,0 e 3,0 mg/L e de hipoclorito de sódio foram 1,0 e 3,0 mg/L. O ácido peracético na concentração de 3,0 mg/L reduziu a carga bacteriana de 1,5x10 (elevado a 5) UFC/mL para 5,24x10 (elevado a 3) UFC/mL. Comparado ao hipoclorito de sódio, o ácido peracético foi menos corrosivo para o aço carbono em todas as concentrações. Na concentração de 1,0 mg/L a taxa de corrosão do cobre em ácido peracético foi menor do que na solução de hipoclorito de sódio. Já na concentração de 3,0 mg/L ocorreu o inverso. Não foi observada corrosão significativa no aço inoxidável para os biocidas estudados. / [en] Microbiological growth in cooling systems water may result in biofilm formation, which can cause problems of bio-corrosion, pressure drop in the pipes, reduction of heat transfer rate and flow obstruction. The main and traditional biocides applied in microbiological control of cooling waters are the chlorine based compounds. However, in recent years, peracetic acid has become an alternative to chlorinated compounds, since this biocide leaves as residue only the acetate, which is biodegradable and does not form chlorinated organic byproducts. This work analyzed the application of peracetic acid comparing to sodium hypochlorite in the microbiological control and material corrosivity using a laboratory scale test tree. The corrosion rate of carbon steel, copper and stainless steel alloys in addition to the effectiveness in reducing the bacterial count. The experiments were carried out under conditions of turbulent flow, pH 8 and temperature of 32 C using a real industrial test water loaded with organics (COD = 350 mg/L). Peracetic acid concentrations used were 0.75, 1.0 and 3.0 mg/L and sodium hypochlorite were 1.0 and 3.0 mg/L. Peracetic acid at the concentration of 3.0 mg/L decreased the bacterial load from 1.5x10 (raised to 5) UFC/mL to 5.24x10 (raised to 3) UFC/mL. Peracetic acid compared to sodium hypochlorite was less corrosive to carbon steel at all concentrations. At the concentration of 1.0 mg/L the corrosion rate of copper in peracetic acid was lower than in sodium hypochlorite solution. At the concentration of 3.0 mg/L, the reverse occurred. No significant corrosion was observed in stainless steel for the biocides studied.

Ce manuscrit présente nos travaux de recherches réalisés sur : i) des éponges marines de Méditerranée (Phorbas tenacior) et des DOM-TOM (Niphates sp. et Clathria rugosa), sélectionnées sur la base des propriétés biologiques préliminaires réalisées sur les extraits bruts, de l’originalité des métabolites, et/ou de l’absence d’étude chimique antérieure de l’espèce ; ii) la synthèse et l’évaluation des propriétés biocides d’analogues de la viscosaline, molécule de type 3-alkylpyridinium aux propriétés antibactériennes et antisalissures faiblement valorisées. L’étude de l’éponge calédonienne Niphates sp. a conduit à l’isolement des népheliosynes A et B, deux polyacétylènes polyhydroxylés avec des cytotoxicités modérées. Les anchinopeptolides B-D, inhibiteurs sélectifs des kinases GSK-3 et PfGSK-3, ont été isolés de Phorbas tenacior, ainsi que la phorbasoïne, un alcaloïde nouveau avec un coeur hydantoïne. Enfin, la première étude chimique de Clathria rugosa a conduit à l’isolement d’un nouveau macrolide, le Clathriolide, un métabolite secondaire cytotoxique vis-à-vis de nombreuses lignées cellulaires tumorales. Chacun des métabolites isolés a fait l’objet d’une étude structurale et biologique poussée. Une stratégie de synthèse originale d’analogues structuraux de la viscosaline a été mise au point. Les dérivés obtenus possèdent d’excellentes activités antibactériennes et antisalissures ainsi que des activités antitumorales modérées. / This manuscript deals with : i) marine sponges from the Mediterranean Sea (Phorbas tenacior) and New Caledonia (Niphates sp. and Clathria rugosa), selected for their biological activities conduced on their crude extract, the originality of produced secondary metabolites and the absence of previous chemical studies ii) the synthesis and the antibacterial properties of analogues of viscosaline. Viscosaline is a 3-alkylpyridinium secondary metabolites which exhibited interesting antibacterial and antifouling properties. The study of the New Caledonian marine sponge Niphates sp. led to the isolation of nepheliosynes Aand B, two polyhydroxylated polyacetylenic acids which exhibited moderate cytotoxic properties. The anchinopeptolides B-D, selective inhibitors of GSK-3 and PfGSK-3 kinases, have been isolated from Phorbas tenacior along with the new alkaloid phorbasoïne. Finally, the first study of the New Caledonian sponge Clathria rugosa let to the isolation of new macrolide, clathriolide, which exhibited cytotoxic properties. The structures and biological properties of each metabolite have been extensively studied in this work. An original synthesis of analogues of viscosaline had been developed. All the derivatives showed excellent antibacterial and antifouling properties, and moderate antitumoral activities.

Les rodenticides anticoagulants (RA) constituent le principal moyen de lutte contre les rongeurs. L’exposition aux RA du renard roux et l’impact des RA sur les populations de ce prédateur sont étudiés. En France, on distingue un contexte « biocide » (BCD) où les RA sont principalement utilisés près des bâtiments et un contexte « phytopharmaceutique » (PP) où la bromadiolone (un RA) est également utilisée en plein champs contre le campagnol terrestre. La contamination des rongeurs aux RA est mesurée : 5 RA sont détectés en contexte BCD alors que la bromadiolone est la molécule majoritaire en contexte PP ; les espèces de rongeurs non ciblées par les RA étant exposées dans les2 contextes. L’exposition est maximale chez les espèces ciblées ou celles au mode de vie similaire.L’exposition du renard est évaluée par la mesure des résidus de RA dans des fèces collectées in situ.La bromadiolone est retrouvée dans 97 % des fèces positives et les RA sont plus retrouvés dans les fèces en cas de traitements PP. En contexte PP, le ratio de fèces positives augmente non linéairement avec la surface traitée dans un rayon d’1 km autour des fèces. L’impact des traitements PP sur les populations de renards est évalué (période 2003-2009, département du Doubs). Les indices d’abondance de renard mesurés sur une commune le printemps d’une année n diminuent avec l’augmentation des quantités d’appâts utilisées les années n-1 et n-2. Pendant la période suivie,la mise en place d’une lutte intégrée contre le campagnol terrestre s’est traduite par une diminution des quantités d’ AR utilisées et donc par une diminution des impacts sur les populations de renards. / Rodents are mainly controlled with anticoagulant rodenticides (AR). AR exposure and impact were studied for red fox populations. In France, we distinguish 2 contexts of AR use: “biocide” (BCD) where AR are used next to buildings and “phytopharmaceutical” (PP) where bromadiolone (an AR) is also applied in the field against the water vole. Rodent contamination to AR was characterized: 5 differentAR were detected in rodents in the BCD context while bromadiolone was predominantly found in thePP context; non target rodents being exposed in both contexts. AR contamination was the highest fortarget species or species with similar lifestyle. Red fox exposure was assessed through themeasurement of AR residues in faeces sampled in the field. ARs were detected more frequently where PP treatments occurred. Every positive faeces contained only bromadiolone except one (BCD context)with chlorophacinone. In PP context, the ratio of positive faeces varied non-linearly with the area of PPtreatments within a 1km-radius around faeces. The impact of bromadiolone PP treatments on red fox populations was assessed (period 2003–2009, Doubs department). Kilometric Abundance Index offoxes measured a year n decreased with higher treatment intensities the years n-1 and n-2. Moreoverwe have shown that a shift to preventive treatments with reduced AR use is less harmful to fox populations.

Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Water-borne coatings often contain multiple additives including pigments, dispersing agents, rheology modifiers, UV stabilizers and biocides. Due to their low molar mass and endocrinedisrupting properties, many of these additives, upon leaching from the substrate film, with time pollute water systems and become hazardous to the environment and to human health. In this study, I aimed to develop a facile method for the production of a polymeric biocide to serve as alternative to low molar mass biocides used in water-borne coatings. A secondary aim was to show that, without additional modification, the polymeric species can be used in surfactant-free ab initio emulsion polymerizations. Using a two-step process, I modified a commercially available copolymer, poly(styrene-alt-maleic anhydride) (SMA 1000), with mixed amines in order to obtain latexes with inherent antimicrobial activity. In the first step, I reacted SMA 1000 with 3-dimethylamino-1-propylamine and aqueous ammonia to confer antimicrobial activity and water-solubility to the SMA copolymer. In the second step, the copolymer was incorporated into a film-forming styrene-butyl acrylate (STY/BuA) latex. The modified SMA was incorporated into a latex in two ways: (1) post-added to the latex, and (2) used as stabilizer in emulsion polymerization. In both cases, the latex remained stable for up to 11 months, and stability was probably due to steric stabilization of the polymer particles. Antimicrobial activity of the latex film was achieved with both methods. When the modified SMA was post-added, antimicrobial activity was restricted to specific areas on the eventual polymer film, and when modified SMA was used as stabilizer, antimicrobial activity was evenly distributed throughout the polymer film. Fluorescence microscopy showed homogeneous distribution of antimicrobial activity upon inoculation in Gram positive bacteria dispersions when the modified copolymer was used as polymeric stabilizer for the synthesis of STY/BuA latexes. No antimicrobial activity against Gram negative bacteria was achieved. The homogeneous distribution of antimicrobial activity throughout the film was a result of adsorption of polymeric biocide/stabilizer to each individual latex particle. With further commercial development, high molar mass copolymers modified for antimicrobial activity may be a feasible, environmentally-friendly and healthy alternative to be used as stabilizers in emulsion polymerizations to produce water-borne coatings. / AFRIKAANSE OPSOMMING: Waterverf bestaan gewoonlik uit ‘n verskeidenheid bestandele, onder andere: pigmente, verspreiding middels, reologie modifiseerders, UV stabiliseerders en biologies aktiewe verbindings. As gevolg van die lae molêre massa en die endokrien ontwrigtende vermoë van baie van die bestandele hou hulle ‘n bedreiging in vir die omgewing in terme van waterbesoedeling en menslike gesondheid, soos hulle die film oor tyd verlaat. In hierdie studie het ek beoog om ‘n eenvoudige metode vir die vervaardiging van ‘n polimeries biologies aktiewe verbindings daar te stel om sodoende as ‘n alternatief vir die lae molêre massa biologies aktiewe verbindings, wat tans in waterverf gebruik word, te dien. ‘n Sekondêre uitkoms van die studie was om te wys dat, sonder enige adissionele omskakelings, dieselfde polimeer gebruik kan word in seep-vrye emulsie polimerisasie. Deur gebruik te maak van ‘n proses, wat uit twee stappe bestaan, het ek ‘n kommersieel beskikbare kopolimeer, poly(stireen-alt-maleinesuuranhidried) (SMA 1000), met gemengde amiene reageer om ‘n sintetiese lateks van stireen en butiel akrilaat (STY/BuA) met inherente antibakteriële aktiwiteit te verkry. In die eerste stap is SMA 1000 met 3-dimetielamien-1-propielamien en waterige ammoniak reageer om ‘n water oplosbare kopolimeer met inherente anti-bakteriële aktiwiteit te verkry. In die tweede stap is hierdie kopolimeer by ‘n sintetiese lateks gevoeg op twee maniere: (1) deur dit nadat die lateks geproduseer is by te voeg, en (2) deur die kopolimeer as stabiliseerder te gebruik in die vervaardiging van die lateks. In albei gevalle is stabiele latekse verkry vir ‘n tydperk van tot 11 maande. Die stabilisering was van steriese geaardheid. Albei die latekse het gevolglik antibakteriële eienskappe getoon. Daar was nie homogene verspreiding van die aktiwiteit in die geval waar die kopolimeer na die tyd bygevoeg is nie en het veroorsaak dat daar sekere areas van die finale film was wat geen aktiwiteit getoon het nie. Fluoresensie mikroskopie het egter homegene verspreiding van die anti-bakteriële aktiwiteit reg deur die film getoon, na inokulasie met Gram positiewe bakterië suspensies wanneer die kopolimeer as polimerisasie stabiliseerder gebruik was. Geen aktiwiteit teen Gram negatiewe bakterië was egter verkry nie. Die homogene verspreiding was as gevolg van die feit dat die kopolimeer sterk adsorbeer op elke individuele lateks partikel wanneer dit as stabiliseerder gebruik word. Verdere ontwikkeling op ‘n kommersiële basis kan daartoe lei dat polimeries biologies aktiewe verbindings as ‘n lewensvatbare en omgewingsvriendelike alternatief vir heidige stabiliseerders in emulsies vir waterverf gebruik kan word.

A indústria naval é uma das mais importantes para economia e desenvolvimento de um país, no entanto, as diversas atividades desenvolvidas em zonas portuárias contribuem para o impacto ambiental a ambientes costeiros, dentre os vários grupos de micropoluentes orgânicos potencialmente danosos a esses ecossistemas, emergiram nos últimos anos os biocidas anti-incrustantes. Pinturas anti-incrustantes são tratamentos utilizados para minimizar processos corrosivos, diminuindo custos com manutenção, economizando combustíveis e reduzindo a veiculação de espécies não nativas entre ecossistemas costeiros. Neste estudo foi desenvolvido, validado e aplicado um método analítico para determinação dos biocidas anti-incrustantes, clorotalonil, diuron, irgarol e tiram em amostras de água, e tecido biológico em diferentes regiões portuárias da costa brasileira e da Ilha de Gran Canaria -Espanha. / The maritime industry is an important aspect of a countries economy, however, the cumulative activities of port areas has an impact on coastal environments, this can include the addition of harmful micro-organic material. Among the potentially harmful micro-organic material being added to ecosystems, are recently emerged anti-fouling biocidal paints. Anti-fouling paints are used as a treatment to minimize corrosive processes, reduce maintenance costs, save fuel and reduce the transmission of non-native species to coastal ecosystems. This study developed, validated and applied an analytical method for the determination of the anti-fouling biocidal paints, chlorothalonil, diuron, irgarol and tiram in water samples and biological tissue in different port areas of the Brazilian coast and the Gran Canaria Island in Spain.