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Techn. Universiẗat, Diss., 2007--Darmstadt.

Reverse osmosis (RO) desalination plants enable the production of high-quality freshwater from seawater, explaining the increasing global use of this technology. However, a major operational challenge for RO is biofouling, caused by excessive biomass accumulation. Membrane fouling simulators (MFSs), downsized membrane systems, were demonstrated to be suitable for biofouling studies using tap water. There is a need to investigate biofouling using natural seawater. The seawater MFS studies involved (i) an exploratory study to evaluate the MFS setup, (ii) long-term operation without feed water nutrient dosage, (iii) impact of nutrient concentration, and (iv) a comparison of biofouling development with freshwater. MFSs were operated parallel at constant feed flow (0.2 m/s), with feed spacer and RO membrane, at varying biodegradable organic nutrient concentrations (0, 50, and 200 µg C/L). The relative pressure drop (RPD) was monitored over time, and biofilm development was characterized through the MFS window applying optical coherence tomography (OCT). Results demonstrated for seawater that (i) the developed setup had a reliable operation and provided reproducible data, (ii) biofouling development presented a minimal effect when nutrient concentration was quadrupled, (iii) there was no correlation between the nutrient concentration and growth rate for seawater experiments, suggesting biofilm development under conditions close to the maximum growth rate. Compared to tap water at the same nutrient concentrations, seawater showed much faster biofilm development, pressure drop increase, and strongly different biofilm morphology. This research provides new insights, new research directions and underlines the importance of doing MFS research with natural seawater.

Membrane distillation (MD) is an emerging thermal separation technology which proved its efficiency in desalination of highly saline waters, including seawater, brines and impaired process waters. In a long-term prospective, MD can reinforce sustainability of the clean water production and mitigate the water-energy stress caused by lacking suitable freshwater recourses. However, just like in any other membrane separation process, MD membrane is susceptible to biofouling which presents a significant challenge by substantially reducing its performance and deteriorating permeate quality. This study evaluated different cleaning methods aimed at controlling biofilm development on a surface of hydrophobic MD membrane in a direct contact MD (DCMD) process fed by the Red Sea water. This was achieved by applying physical (hydraulic) cleaning and chemical cleanings with a range of chemicals utilized in membrane separation processes including citric acid (mineral acid), ethylenediaminetetraacetic acid (EDTA, metal-chelating agent) and sodium hypochlorite (NaOCl, oxidant). Flux recovery and changes in biofilm morphology, including its thickness and structure as well as microbial and extracellular polymeric substances (EPS) contents before and after cleanings have been analyzed to elucidate cleaning mechanisms and suggest effective strategies of biofilm removal. The results showed that 0.3% EDTA exhibited the best cleaning performance resulting in the highest permeate flux recovery (93%), followed by 0.3% NaOCl (89%), 3% citric acid (76%), and hydraulic (66%) cleanings. Application of EDTA and NaOCl has also resulted in the lowest number of bacterial cells and substantial reduction of the peak intensities caused by protein-like compounds and tyrosine-containing proteins present on the membrane surface after its treamtent. The observed trends are in a good correlation with the optical coherence tomography (OCT) observations which revealed substation changes in biofilm morphology leading to a significant reduction of biofilm thickness which followed the order of hydraulic cleaning < citric acid cleaning < NaOCl cleaning < EDTA cleaning. This study suggests that selection of an appropriate cleaning type and formulation is critical for achieving sustainable MD plant operations, both technically and economically.

Invasive colonial tunicates pose substantial economic threat to the shellfish aquaculture industry, but their population dynamics and ecological impacts are highly variable and region-specific. This thesis contributes to our regional understanding of two such tunicates in Oregon. The first chapter explores the population dynamics of Didemnum vexillum, one of Oregon’s top 100 most dangerous invasive species, at an oyster farm. From May 2011 to 2016 the population fluctuated extensively, though did not exhibit any net growth over the study period. In the second chapter, I demonstrate that Botrylloides violaceus had no impact on the growth, condition, or organic composition of oysters and mussels grown in a simulation of longline aquaculture. Together, these studies paint a cautiously positive outlook for the shellfish aquaculture industry in Oregon. This thesis includes previously unpublished co-authored material.

The overall emphasis of this doctoral dissertation is on the design, synthesis, detailed characterization and application of amphiphilic hyperbranched fluoropolymers (HBFPs) crosslinked with poly(ethylene glycols) (PEGs) in complex polymer coatings as anti-biofouling surfaces. This dissertation bridges synthetic polymer chemistry, materials science and biology to produce functional coatings capable of fouling prevention, demonstrating thermo-controlled healing and acting as a benchmark surface to understand component:property relationships prior to increasing formulation complexities. A two-dimensional array of HBFP-PEG coatings was produced by the co-deposition of uniquely composed HBFPs with varying weight percentages of PEG. Bulk and surface properties were evaluated and assigned to formulation trends. Based on these findings, the most viable candidates were replicated and their fouling responses were assessed against three marine fouling organisms. An active mode of biofouling resistance was covalently grafted onto the surface of HBFP-PEG. The presentation of the settlement-deterrent molecule noradrenaline (NA) works in tandem with the highly-complex surface, to act as a dual-mode, anti-biofouling coating NA-HBFP-PEG. Secondary ion mass spectrometry (SIMS) was employed to quantify the extent of NA substitution. Biological assays against oyster hemocytes confirmed the activity of the grafted NA and cyprid settlement assays supported that the overall anti-biofouling ability of NA-HBFP-PEG was increased by 75%. Thermally-reversible crosslinks were installed as healable units throughout the framework of the networks, with the goal of generating coatings that could possess a greater resistance to mechanical failure. Small molecule and linear polymer models were probed by nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC) to demonstrate the controlled reversibility of the crosslinks. Optical microscopy was employed to visualize surface scratch healing and fluorescence microscopy was used to identify the adsorption behavior of fluorescently-labeled proteins. A benchmark, anti-biofouling surface was generated through thiol-ene crosslinking of a linear fluoropolymer with pendant alkenes (LFPene) with pentaerythritol tetrakis(3-mercaptopropionate) (PETMP). Core constituents were evaluated spectroscopically and surfaces of LFPene-PETMP, along with two model surfaces that largely expressed a single component, were analyzed to understand how individual elements and blending contributed to the physical, mechanical and anti-biofouling properties to generate a performance baseline to compare against future generations.

The use of seawater in cooling towers for industrial applications has much merit in the Gulf Cooperation Council countries due to the scarcity and availability of fresh water. Seawater make-up in cooling towers is deemed the most feasible because of its unlimited supply in coastal areas. Such latent-heat removal with seawater in cooling towers is several folds more efficient than sensible heat extraction via heat exchangers. Operational challenges such as scaling, corrosion, and biofouling are a major challenge in conventional cooling towers, where the latter is also a major issue in seawater cooling towers. Biofouling can significantly hamper the efficiency of cooling towers. The most popular methods used in cooling treatment to control biofouling are disinfection by chlorination. However, the disadvantages of chlorination are formation of harmful disinfection byproducts in the presence of high organic loading and safety concerns in the storage of chlorine gas. In this study, the research focuses on biofouling control in seawater cooling towers by investigating two different approaches. The first strategy addresses the use of alternative oxidants (i.e. ozone micro-bubbles and chlorine dioxide) in treatment of cooling towers. The second strategy investigates removing nutrients in seawater using granular activated carbon filter column and ultrafiltration to prevent the growth of microorganisms. Laboratory bench-scale tests in terms of temperature, cycle of concentration, dosage, etc. indicated that, at lower oxidant dosages (total residual oxidant (TRO) equivalent = 0.1 mg/l Cl2), chlorine dioxide had a better disinfection effect than chlorine and ozone. The performance of oxidizing biocides at pilot scale, operating at assorted conditions, showed that for the disinfectants tested, ozone could remove 95 % bioactivity of total number of bacteria and algae followed by chlorine dioxide at 85%, while conventional chlorine dosing only gave 60% reduction in bioactivities. Test results of GAC bio-filter showed that around 70 % removal of total organic carbon in the seawater feed was achieved and was effective in keeping the microbial growth to a minimum. The measured results from this study enable designers of seawater cooling towers to manage the biofouling problems when such cooling towers are extrapolated to a pilot scale.

Biofouling is a significant economic problem, particularly for marine and offshore oil industries. The acorn barnacle (Amphibalanus (Balanus) amphitrite) is the main biofouling organism in marine environments. Environmental conditions, the physiology of the biofouling organism, the surrounding microbial community, and the properties of the substratum can all influence the attachment of biofouling organisms to substrates. My dissertation investigated the biological processes involved in B. amphitrite development and attachment in the unique environment of the Red Sea, where the average water surface temperature is 34°C and the salinity reaches 41‰. I profiled the transcriptome and proteome of B. amphitrite at different life stages (nauplius II, nauplius VI, and cyprid) and identified 65,784 expressed contigs and 1387 expressed proteins by quantitative proteomics. During the planktonic stage, genes related to osmotic stress, salt stress, the hyperosmotic response, and the Wnt signaling pathway were strongly up-regulated, hereas genes related to the MAPK pathway, lipid metabolism, and cuticle development were down-regulated. In the transition from the nauplius VI to cyprid stages, there was up-regulation of genes involved in blood coagulation, cuticle development, and eggshell formation, and down-regulation of genes in the nitric oxide pathway, which stimulates the swimming and feeding responses of marine invertebrates. This system-wide integrated approach elucidated the development and attachment pathways important in B. amphitrite. Enzymes and metabolites in these pathways are potential molecular targets for the development of new antifouling compounds.

Bubbles are commonly found in the world around us, from industrial products to carbonated beverages. This thesis will discuss three processes involving of bubbles, from applications to fundamental phenomena. In the first portion of this thesis, I describe the use of bubbles to prevent the formation of marine biofilms and other colonizing organisms onto built structures, collectively referred to as biofouling. Biofouling detrimentally affects the structures upon which they grow, increasing drag and fuel consumption of moving vessels, reducing performance of acoustic sensors, and enhancing degradation of static structures. With recent international bans placed on common biocidal coatings, there is a demand for environmentally friendly antifouling technologies with strong performance. Bubbles rising along a submerged surface have been shown to inhibit biofouling growth, but little work has been done to determine the primary mechanisms responsible for their antifouling behavior. In this thesis I discuss a combination of field and laboratory experiments as well as a theoretical approach used to gain insight into the dominant mechanisms at play, thus laying a foundation for optimization of this antifouling technique. We find that biofouling is inhibited by shear stresses generated throughout the flow, and the degree of biofouling prevention relates to the distribution of bubbles which locally alters the shear stress. Inspired by the potential for direct interactions between bubbles and biofouling, the second topic of this thesis considers the process by which a bubble dewets, or "sticks to", a solid surface. As a bubble approaches a solid surface, the liquid between the gas and solid begins to drain until it resembles a thin film. Upon rupture of this thin film, the air dewets the surface as a contact line is formed and expands. Previous work regarding this contact line motion assumes viscous effects dominate the spreading dynamics while inertial effects are neglected. Studying the early-time dynamics of dewetting bubbles, we find viscosity to be negligible while inertia and capillarity govern the motion of a newly established contact line, suggesting early stages of dewetting are more rapid than anticipated. In the final portion of this thesis, I discuss the fundamental stability of bubbles in volatile liquids. When a bubble arrives at a free surface, we typically expect the film of the bubble cap to thin over some period of time until it ruptures. Traditionally, the drainage of this film has been considered inevitable with evaporation only hastening the film rupture. Here I show air bubbles at the free surface of liquids which appear to defy traditional drainage rules and can avoid rupture, persisting for hours until dissolution. Using pure, volatile liquids free of any surfactants, we highlight and model a thermocapillary phenomenon in which liquid surrounding the bubble is continuously drawn into the bubble cap, effectively overpowering the drainage effects. / 2020-09-28T00:00:00Z

Biofouling and biocorrosion are due to unwanted deposition of microorganisms on surfaces that are exposed to different types of water. This dissertation focuses on the application of innovative strategies to inhibit biofouling and biocorrosion. Specifically, the strategies examined in this dissertation, namely the use of bacteriophages and quorum quenchers, aim to minimize reliance on the conventional chemical cleaning agents and to reduce chemical-induced hazards on health, safety and environment. First, we analyzed the use of bacteriophages to remove biofoulants on ultrafiltration membrane used in seawater reverse osmosis pretreatment. Our findings revealed that bacteriophages were able to remain active against membrane-associated Pseudomonas aeruginosa at a broad range of temperature, pH and salinity. Bacteriophages were also shown to inhibit biofilm and to reduce transmembrane pressure increment, when applied alone or in combination with chemical agents. Second, this dissertation explores the use of quorum quenchers to inhibit biocorrosion in seawater environment. To do so, we first examined for the presence of quorum sensing system in sulfate reducing bacteria (SRB). Through transcriptomic analysis, we further demonstrate a strong correlation between quorum sensing, biofilm formation and biocorrosion. Therefore, the use of quorum sensing inhibitors was suggested to prevent biofilm formation and biocorrosion caused by SRB in seawater. Through findings from Chapter 2 and 3, we introduced the use of alternative biocidal agents to tackle biofouling and biocorrosion. Compared to quorum quenchers, bacteriophages showed better antibiofilm potential and easier applicability at larger scale. However, bacteriophages alone were insufficient to reduce biofilm formation as phage resistance was observed over long-term experiments. Hence in the last chapter, we further explored the use of bacteriophages to alleviate biofouling that occurred during wastewater treatment process, by combining their infection with UV irradiation. UV was used both for its biocidal effect and to trigger phage infection against bacteria. Our findings indicate that the combined treatment was able to remove mature biofoulants from the membrane. Overall, this dissertation demonstrates the use of bacteriophages and quorum quenchers against biofilm. These two approaches can serve to reduce the amount of chemicals used during cleaning, thus providing a more sustainable way of minimizing biofilm-associated problems.