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.

Det har uppmärksammat att det fortfarande förekommer tenn och koppar från båtbottenfärg på fritidsbåtars skrov trots förbud av båtbottenfärger med tennföreningen TBT sedan 1989 och reglering av kopparbaserade färger sedan 1999.Syftet med denna kandidatuppsats är att ge en dagslägesrapport vad gäller förekomst av tenn och koppar på fritidsbåtars skrov.Under våren 2011 har tester på 336 fritidsbåtar i tre vattenområden gjorts med hjälp av en handhållen XRF (X-Ray Fluorescence, röntgenfluorescens) som genom avläsning av en yta visar halter av olika grundämnen. Testerna utfördes på vinterförvarade fritidsbåtar <12 m hos båtklubbar vid Mälaren, Storsjön och Härnösandskusten. Undersökningen visar att 73 % av båtarna i denna undersökning har halter av tenn och/eller koppar överstigande >2500 ppm, vilket är det för rapporten satta riktvärdet. Det innebär att de skulle kunna tas vidare till kemisk testning med till exempel gaskromatografi kopplad till masspektrometri (GC-MS) för att avgöra exakt vilken substans färgen innehåller. Resultatet visar också att användningen av tennfärger antingen fortfarande förekommer i liten skala eller att gamla tennfärger är så pass starka att de ger utslag genom övermålade färglager. Kopparfärg verkar användas både vid ostkusten och i insjöar.Antifoulingsystem som kan ersätta bottenfärg blir allt vanligare och det dyker upp fler och fler mer miljövänliga alternativ på marknaden. Det vanligaste alternativa systemet, båttvättar, blir dock mindre miljövänligt i och med förekomst av gammal färg innehållande skadliga substanser som tvättas av i båtborsttvättar med starkt bristfällig uppsamling och rening av avfallet/slammet. / It has been noticed that tin and copper are still present in antifouling paints residing on the hulls of leisure boats, in spite of a ban of TBT-based paints since 1989 and strict regulations regarding copper-based paints since 1999.This bachelor thesis aims to give the reader a view of the current situation regarding the presence of tin and copper on the hull of leisure boats.During the spring of 2011, 336 leisure boats in three different waters were tested with a hand-held XRF analyzer (X-Ray Fluorescence). After scanning the surface of a hull the machine displays the paint’s proportions of basic elements. Testing was performed on leisure boats, winter-stored at yacht clubs connected to the lakes Mälaren, Storsjön and the coast of Härnösand. In this study 73 % of the tested boats show levels of tin and/or copper exceeding the (for this essay) set limits of 2500 parts per million, which means they could qualify for further testing, gas chromatography coupled to mass spectrometry (GC-MS) for example, to determine the exact substances in the paints. The results also show that tin-based paints are either still in use, albeit in small scale, or that they are strong enough to detect through another layer(s) of paint. Copper-based paints seem to be used both along the east coast and in fresh-water lakes.More and more alternative antifouling systems that are capable of replacing paints while being more environmentally friendly are reaching the market. The most common alternative, to wash the boat with brushes or with a high-pressure water jet, is somewhat less environmentally friendly when the boat is painted with harmful substances and the facilities lack proper collection and sanitation of the wastewater.

Membrane-based filtration and separation processes are widely used in various fields, such as for clean drinking water, food, dairy industry, medical, biotechnology, and environmental applications. Providing clean and safe drinking water has been regarded as one of the global biggest challenges because of increasing world population, impacts of climate changes, increased wastewater production, and increased contamination of surface and groundwater. The most important technologies contributing substantially in this field are based on pressure-driven membrane technologies such as microfiltration, ultrafiltration, nanofiltration, and reverse osmosis. Recently, in situ synthesis of nanoparticles based on molecular level design and tailoring in the membrane matrix have been reported to prepare next generation nano-enhanced membranes. In this work similar technique was utilized to construct PSF-Silica nanocomposite membranes in which hydrolysis and condensation of silica precursor (TEOS, APTES, and TPAPS) and phase inversion of polymer film was achieved simultaneously in one step under acidic condition. This unique process has led to the formation of extremely small silica nanoparticles with high dispersion in every region of the membrane. Such type of distribution of silica nanoparticles is very difficult to achieve using conventional silica nanoparticle blending with polymer solution. The prepared membranes were extensively characterized for their morphology, surface properties, nanoparticle distribution, fouling and permeation properties. Finally, the membranes were tested with rejection experiments with protein and dye solutions to assess their usefulness for water filtration and separation applications. The silica nanoparticles were mostly generated during the phase inversion under acidic condition by hydrolysis and polycondensation reaction of silica precursors mixed with PSF solution. The properties and structure of membranes were characterized by different analytic and physicochemical techniques. The prepared membranes exhibit an asymmetric nature with a dense skin layer, followed by finger-like porous structure at the bottom. The microscopic and elemental analysis confirmed the presence and homogeneous distribution of nanoscopic small silica particles throughout the membrane matrix. Hydrophilic SiO2, SiO2-NH2, SO2-NH-SO3H nanoparticles were respectively formed in situ within PSF membrane matrix during the phase inversion under acidic condition by hydrolysis and polycondensation reaction of corresponding silica precursors mixed with PSF solution. Because the nanosize and good distribution of the pores, the presence and well distribution of silica nanoparticles, the presence and exposure of the hydrophilic charged functional groups form a hydrate layer on the membranes and provide hydration repulsion and electrostatic repulsion against solutes from feed under aqueous medium, the PSF-TEOS, PSF-APTES, PSF-TPAPS membranes respectively with SiO2, SiO2-NH2, and SO2-NH-SO3H nanoparticles exhibited high hydrophilicity, stability, water permeation, rejection, and antifouling performance as compared to the neat PSF membrane for water purification application. The overall membrane properties were highly dependent on the concentration of the silica nanoparticles and can be tuned by adjusting the concentration of initial silica precursors during membrane formation. The low protein fouling, high water permeation, protein rejection, and flux recovery results make those membranes attractive for separation and filtration applications. Thus, the prepared membranes can be used in different applications ranging from separation of biomolecules, desalination/purification of water, and for other charge and size-based separation processes.

Biocide-based antifouling (AF) paints are the most common method for preventing biofouling, i.e. the growth of algae, barnacles and other organisms on boat hulls. AF paints for leisure boats are predominantly based on copper (Cu) as the main biocide, with zinc (Zn) present as a pigment and stabilizer. Both metals are released from the paint matrix into the water column, leading to contamination of marinas which typically have only limited water exchange. Thus, the aim of this PhD thesis was to describe the use of AF paints in different regions in Sweden, as well as the associated environmental consequences with regard to contamination of the environment and toxicity to non-target aquatic snails. Using a recently developed X-ray fluorescence application, high levels of Cu were detected on boats moored in freshwaters, despite a more than 20-year-old ban, as well as high levels of tin (Sn) on 10 % of the boats, indicating the presence of (old) tributyltin paints (TBT), which might pose an environmental risk and a health hazard for people performing the paint scraping (paper 1). In addition, very high levels of Cu and Zn were measured in the biofouling material collected from the boat hulls, and this is problematic because the biofouling is commonly disposed of on the soil in boatyards at the end of each season. No difference was found in the amount of biofouling on boats coated with Cu or biocide-free paints, which implies that Cu might be currently overused in areas of low salinity and low barnacle density (paper 2). This work also introduces the use of a new species for ecotoxicological field experiments, the snail Theodoxus fluviatilis. Chronic field experiments (paper 3) revealed 6-fold increases in snail mortality, negative growth and up to 67-fold decreased reproduction in marinas, compared to areas not impacted by boating (‘reference areas’). Moreover, a higher prevalence of snails with histopathological alterations (e.g. necrosis of gills, gonads, midgut gland and parasite infestation, among others) was observed in the marinas, compared to the reference areas (paper 4). Statistical modelling indicated that the majority of the toxic effects were best predicted by the metals, most likely originating from AF paints. The results presented in this thesis depict some important aspects of AF paint use in brackish water and highlight the necessity of implementing a suitable management practice for the heavily contaminated biofouling waste in order to minimize the risk to soils. In addition, the evidence of toxicity to snails in marinas can be used as a basis to increase the public understanding of the impact of recreational boating and encourage people to choose less toxic alternatives to AF paints. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.</p>

Tout support immergé dans l’eau est rapidement colonisé par de nombreux organismes micro- et macroscopiques. Ce phénomène séquentiel et complexe appelé biofouling est à l’origine de nombreux préjudices économiques et écologiques, notamment dans le milieu marin. L’interdiction récente de certaines substances toxiques, utilisées comme biocides dans les revêtements antifouling des coques de bateaux notamment, a relancé l’intérêt de rechercher de nouvelles molécules antifouling respectueuses de l’environnement. L’objectif de cette thèse a été de développer et d’amorcer l’étude de la représentativité d’un bio-essai permettant d’évaluer le potentiel antifouling de molécules et de revêtements sur des « biofilms » mono et plurispécifiques in vitro en microplaques grâce à l’utilisation de fluorochromes. Le choix a été fait de se focaliser sur le biofilm primaire car il est envisagé que l’élimination ou la limitation de ce dernier réduisent le biofouling. Cinq souches de bactéries marines pionnières, isolées de la Rade de Toulon et en Bretagne, ont été utilisées afin de comparer l’efficacité anti-adhésion de molécules commerciales et naturelles. Deux dérivés de synthèse de substances naturelles marines (TFA E et Z) ont présenté une activité significative associée à une absence de toxicité sur bactéries, suggérant ainsi un mode d’action anti-adhésion spécifique. En outre, les différences de sensibilité entre souches ont confirmée l’importance de réaliser le bio-essai avec un panel diversifié de bactéries.Afin de voir si les données obtenues en laboratoire reflétaient ce qui se produit dans le milieu naturel, une comparaison entre les résultats du bio-essai en microplaque appliqué à six revêtements et les biofilms qui ont colonisés ces mêmes peintures immergées un mois dans la Rade de Toulon (analysés par cytométrie de flux, microscopie et PCR-DGGE), a été effectuée. Les analyses quantitatives ont suggéré une cohérence entre les deux approches même si l’absence de revêtement d’efficacité intermédiaire et le nombre de systèmes testés limite la portée de nos conclusions / Any surface immersed in water is rapidly colonized by a lot of micro-and macroscopic organisms. Sequential and complex phenomenon known as biofouling, lead to major economic and ecological damages, particularly in the marine environment. The recent ban of toxic substances used as biocides in antifouling coatings for ship hulls notably, has relaunched searching for new molecules antifouling environmentally friendly. The objective of this thesis was to develop and initiate the study of the representativeness of a bioassay allow to assess the potential of molecules and antifouling coatings on "biofilms" mono and multi-species microplate using of fluorochromes. It was decided to focus on the primary biofilm because it is possible that the elimination or limitation of the latter reduce biofouling. Five strains of marine bacteria pioneers, isolated from the Bay of Toulon and Brittany, were used to compare the effectiveness of a settlement of commercial and natural molecules. Two derivatives of natural substances Marine (TFA E and Z) showed significant activity associated with a lack of toxicity in bacteria, suggesting a specific anti-adhesion mechanism. In addition, differences in sensitivity between strains have confirmed the importance of making the bioassay with a various bacteria. To see if the data obtained in the laboratory showed what happens in the natural environment, a comparison between the results of the bioassay in microplate applied to six coatings and biofilms isolated on the same paint immersed for a month in the Bay of Toulon (analyzed by flow cytometry, microscopy and PCR-DGGE) was performed. Quantitative analysis suggested a correlation in between approaches although the absence of effectiency intermediate coating and the number of tested systems limit our conclusions

Copper (Cu) is a heavy metal that is essential for life but toxic at high concentrations. This toxic effect is used on boats to prevent biofouling on boat hulls by painting the hulls with antifouling paint that contain high levels of Cu. The Cu is slowly diffused out in the water and accumulated by animals higher up in the food chain. In order to test the effects of marinas on Cu bioaccumulation in invertebrates, I sampled molluscs at seven marinas and seven shore sites on the Swedish west coast. Two molluscs with different feeding behaviours, one grazer, the periwinkle (Littorina littorea) and one filter feeder, the blue mussel (Mytilus edulis) were used as study organisms. Both species were sampled at each location within 50 m from each other. Body Cu concentration of both species was measured with a Flame Atomic Absorption Spectrometer (FAAS). Cu concentration of periwinkle soft body tissue was generally higher than in mussel soft body tissue. In addition, periwinkle tissue Cu concentration reacted strongly positively to the presence of marinas, whereas mussel tissue Cu concentrations did not. This shows that contamination from marinas affects the grazing periwinkle but not the filter feeding blue mussel. Thus, for biomonitoring purposes, grazers may be more suited as indicator organisms.

La biomasse des microalgues tropicales a des vertus naturelles qui peuvent être utilisées dans une large gamme de bioproduits. Leur valorisation peut permettre une production durable et commercialement viable. En effet, les microalgues tropicales représentent une grande biodiversité et bénéficient de conditions environnementales favorables à une production à grande échelle. Dans ce contexte, cette thèse vise à étudier de nouvelles souches tropicales afin de connaître leur potentiel de valorisation dans le domaine des biotechnologies, et plus particulièrement sur trois aspects : énergie, nutraceutique et antifouling. Ce dernier domaine a été étudié dans le cadre du projet ANR-CD2I « BIOPAINTROP » dont l’objectif est la lutte écoresponsable contre le biofouling. Ces travaux s’orientent vers des applications biotechnologiques, mais aussi vers le développement des nouvelles méthodes de caractérisation de l’activité antifouling. Sur les 50 souches étudiées, certaines ont montré la production de métabolites d'intérêt tels que le glycosylglycerol, des lipides de qualité pour la nutraceutique et la production de biodiesel. La souche Amphidinium sp. (P-43) a conduit à un extrait méthanolique possédant une activité biologique significative. Son efficacité dans la lutte contre le biofilm a été démontrée. De plus, l'étude d'écotoxicologie réalisée laisse présager d'un faible impact environnemental. / Biomass of tropical microalgae have natural virtues that can be used in a wide range of bioproducts. Their valuation can enable sustainable and commercially viable production. Indeed, tropical microalgae represent a large biodiversity and benefit from favourable environmental conditions for large scale production. In this context, this thesis aims to explore new tropical strains to determine their potential development in the field of biotechnology, particularly in three areas: energy, nutraceutical and antifouling. This field is studied in the project ANR-CD2I "BIOPAINTROP" whose objective is the eco-responsible fight against biofouling. These works target biotechnological applications, but also development of new methods to characterize antifouling activity.Of the 50 strains studied, some have shown interest in the production of metabolites such as glycosyl glycerol, quality nutraceutical and lipids for biodiesel production. The Amphidinium sp. (P-43) stain led to a methanol extract having biological activity of interest. Its efficiency against biofilm was demonstrated. Moreover, the ecotoxicology study has suggested a low environmental impact.

Alors que les premières formes de vie sont apparues dans les océans il y a près de 4 milliards d'années, les premières espèces terrestres remontent seulement à 400 millions d'années. Malgré cela, les substances naturelles d'origine marine ne représentent que 10% de l'ensemble des molécules isolées à ce jour à partir d'organismes vivants. Ces composés chimiques sont pourtant très spécifiques du fait des particularités du Monde Marin. Au sein des organismes qui les biosynthétisent, ils peuvent notamment intervenir dans la défense chimique contre les parasites et les autres compétiteurs. Ces molécules apparaissent donc comme des alternatives potentielles aux oxydes du tributylétain (TBTO) présents dans les revêtements antifouling et interdits depuis 2008 en raison de leur toxicité. Dans ce contexte et dans le cadre d'un partenariat avec le Parc national de Port-Cros, l'étude de la composition chimique de plusieurs organismes marins méditerranéens, des algues vertes (Caulerpa taxifolia) et brunes (Dictyota sp., Dictyota dichotoma, Cystoseira foeniculacea) ainsi que des bryozoaires, a été entreprise. Ces travaux ont permis l'isolement et la caractérisation structurale d'une vingtaine de métabolites secondaires (dérivés terpéniques et lipidiques, stérols), parmi lesquels huit sont originaux. L'identification de l'ensemble de ces molécules a été réalisée par le biais de l'utilisation de différentes méthodes spectroscopiques (RMN 1D et 2D, SM-HR) et la stéréochimie de certaines d'entre-elles a été établie par RMN (expérience NOESY 1H-1H) et modélisation moléculaire. Des corrections de données spectrales ont été également proposées pour cinq composés connus. Par ailleurs, l'activité anti-adhésion de plusieurs métabolites issus d'algues a été évaluée vis-à-vis d'un biofilm bactérien marin (Pseudoalteromonas sp.) afin de déterminer leur potentiel en tant qu'agents antifouling : plusieurs de ces composés présente une activité intéressante (CE50 = 30 μM), certes inférieure à celle du TBTO (CE50 = 10 μM), mais largement supérieure à celles de co-biocides utilisés actuellement. Parallèlement à ces travaux, l'analyse des variations temporelles et spatiales de l'expression métabolique de certaines des espèces étudiées a été réalisée à des fins écologiques. D'une part, les extraits mensuels de C. taxifolia présentent généralement une activité anti-adhésion importante quand le taux de caulerpényne dans l'extrait est élevé. D'autre part, d'importantes fluctuations ont notamment été observées dans la composition chimique des bryozoaires Myriapora truncata et Pentapora fascialis en fonction de leur lieu de récolte.

Thesis (Ph. D.)--University of California, San Diego, 2007. / Title from first page of PDF file (viewed October 2, 2007). Available via ProQuest Digital Dissertations. Vita. Includes bibliographical references (p. 88-93).

Os processos de separação com membranas estão presentes nas mais diversas aplicações industriais. Em especial, a microfiltração e a ultrafiltração vêm sendo extensivamente utilizadas no tratamento de água e de efluentes. Com o aumento da demanda, muitos estudos têm sido feitos para melhorar o desempenho dos processos com membranas, porém a escolha apropriada da membrana é um fator crucial para atingir esse objetivo. As membranas à base de polietersulfona (PES) estão entre as mais utilizadas industrialmente para esse tipo de aplicação devido às suas excelentes propriedades mecânicas, estabilidade térmica e resistência química. No entanto, por serem pouco hidrofílicas, essas membranas apresentam baixos fluxos de água e elevada tendência ao fouling e ao biofouling. A fim de melhorar essas propriedades, muitos autores têm proposto modificações nas membranas para torná-las mais hidrofílicas e, portanto, aumentar o fluxo de água e diminuir o fouling. Dentro desse contexto, o presente trabalho teve como objetivo preparar membranas de ultrafiltração de PES, utilizando a ftaloil-quitosana (FQ) como aditivo, a fim de se obter membranas com propriedade antifouling. Membranas de PES e PES/FQ foram preparadas pelo processo de inversão de fases e caracterizadas quanto à morfologia, à estrutura química, à estabilidade térmica, ao caráter hidrofílico, à permeância hidráulica, à massa molar de corte (MMC) e ao desempenho em ultrafiltração de solução proteica. As membranas modificadas com o aditivo apresentaram estrutura mais heterogênea e com macrovazios maiores, maior caráter hidrofílico e maior permeância hidráulica. Os resultados de MMC não foram conclusivos. No teste de ultrafiltração, essas membranas apresentaram maiores fluxos e menor tendência ao fouling, indicando que o aditivo utilizado foi adequado na melhoria das propriedades desejadas. A retenção proteica, a perda de fluxo e a recuperação de fluxo após limpezas não apresentaram diferenças significativas. / In recent years, membrane separation processes have been widely used in all kinds of industries and applications. Particularly microfiltration and ultrafiltration have been extensively used for drinking water and wastewater treatments. With the increasing demand, many efforts have been done in order to enhance the process performance, but the choice of the appropriate membrane is a crucial factor to achieve this goal. Polyethersulfone (PES) based membranes are among the most commonly used for such applications due to their excellent chemical resistance, thermal stability and mechanical properties. However, because of its low hydrophilicity, these membranes have low water flux and high fouling and biofouling tendency. In order to improve these properties, many authors have proposed membrane modifications to make them more hydrophilic and thus increase the water flux and reduce fouling. Within this context, this work aimed to prepare PES ultrafiltration membranes using phthaloyl-chitosan (FQ) as an additive in order to obtain membranes with antifouling property. PES and PES/FQ membranes were prepared by phase inversion process and their morphology, chemical structure, thermal stability, hydrophilicity, hydraulic permeance, molecular weight cutoff (MWCO) and performance in ultrafiltration of protein solution were characterized. The membranes modified with additives showed more heterogeneous structure with larger macrovoids, higher hydrophilicity and higher hydraulic permeance. The MWCO results were inconclusive. In the ultrafiltration test, these membranes exhibited higher fluxes and lower fouling tendency, indicating that the additive used was adequate in improving the desired properties. The protein retention, flux reduction and flux recovery after cleaning showed no significant differences.