Yes / Scale formation of carbonates and sulphates is one of the most well-known types of crystallization fouling in heat exchangers. Tackling crystallization fouling in Once-Through Multistage Flash Desalination (MSF-OT) is one of the most challenging tasks in the desalination industry. In this paper, a fouling model is developed and then incorporated into a MSF model to investigate the fouling behaviour under variable seawater temperature. The proposed dynamic model investigates the crystallization of calcium carbonate and magnesium hydroxide at the inside tube surface areas by considering the attachment and removal mechanisms. The results show that the fouling rate is higher at high constant seawater temperature. Overall, the fouling rate is lower at the seasonal variation of the seawater temperature, resulting in a higher performance ratio (PR). The results also show that although the brine heater duty increases in winter due to low seawater temperature, the drop of fouling rate in cold months may save some energy.

Among many seawater desalination processes, the multistage flash (MSF) desalination process is a major source of fresh water around the world. The most costly design and operation problem in seawater desalination is due to scale formation and corrosion problems. Fouling factor is one of the many important parameters that affect the operation of MSF processes. This thesis therefore focuses on determining the optimal design and operation strategy of MSF desalinations processes under fouling which will meet variable demand of freshwater. First, a steady state model of MSF is developed based on the basic laws of mass balance, energy balance, and heat transfer equations with supporting correlations for physical properties. gPROMS software is used to develop the model which is validated against the results reported in the literature. The model is then used in further investigations. Based on actual plant data, a simple dynamic fouling factor profile is developed which allows calculation of fouling factor at different time (season of the year). The role of changing brine heater fouling factor with varying seawater temperatures (during the year) on the plant performance and the monthly operating costs for fixed water demand and fixed top brine temperature are then studied. The total monthly operation cost of the process are minimised while the operating parameters such as make up, brine recycle flow rate and steam temperature are optimised. It was found that the seasonal variation in seawater temperature and brine heater fouling factor results in significant variations in the operating parameters and operating costs. The design and operation of the MSF process are optimized in order to meet variable demands of freshwater with changing seawater temperature throughout the day and throughout the year. On the basis of actual data, the neural network (NN) technique has been used to develop a correlation for calculating dynamic freshwater demand/consumption profiles at different times of the day and season. Also, a simple polynomial based dynamic seawater temperature correlation is developed based on actual data. An intermediate storage tank between the plant and the client is considered. The MSF process model developed earlier is coupled with the dynamic model for the storage tank and is incorporated into the optimization framework within gPROMS. Four main seasons are considered in a year and for each season, with variable freshwater demand and seawater temperature, the operating parameters are optimized at discrete time intervals, while minimizing the total daily costs. The intermediate storage tank adds flexible scheduling and maintenance opportunity of individual flash stages and makes it possible to meet variable freshwater demand with varying seawater temperatures without interrupting or fully shutting down the plant at any-time during the day and for any season. Finally, the purity of freshwater coming from MSF desalination plants is very important when the water is used for industrial services such as feed of boiler to produce steam. In this work, for fixed water demand and top brine temperature, the effect of separation efficiency of demister with seasonal variation of seawater temperatures on the final purity of freshwater for both cleaned and fouled demister conditions is studied. It was found that the purity of freshwater is affected by the total number of stages. Also to maintain the purity of freshwater product, comparatively large number of flash stage is required for fouled demister.

Biocatalytic membrane reactors combine the highly efficient biotransformation capability of enzymes with the selective filtration performance of membrane filters. Common strategies to immobilize enzymes on polymeric membranes are based on chemical coupling reactions. Still, they are associated with drawbacks such as long reaction times, high costs, and the use of potentially toxic or hazardous reagents. In this study, a reagent-free immobilization method based on electron beam irradiation was investigated, which allows much faster, cleaner, and cheaper fabrication of enzyme membrane reactors. Two industrial lipase enzymes were coupled onto a polyvinylidene fluoride (PVDF) flat sheet membrane to create self-cleaning surfaces. The response surface methodology (RSM) in the design-of-experiments approach was applied to investigate the effects of three numerical factors on enzyme activity, yielding a maximum activity of 823 118 U m2 (enzyme concentration: 8.4 g L1, impregnation time: 5 min, irradiation dose: 80 kGy). The lipolytic membranes were used in fouling tests with olive oil (1 g L1 in 2 mM sodium dodecyl sulfate), resulting in 100% regeneration of filtration performance after 3 h of self-cleaning in an aqueous buffer (pH 8, 37 C). Reusability with three consecutive cycles demonstrates regeneration of 95%. Comprehensive membrane characterization was performed by determining enzyme kinetic parameters, permeance monitoring, X-ray photoelectron spectroscopy, FTIR spectroscopy, scanning electron microscopy, and zeta potential, as well as water contact angle measurements.

Membrane bioreactors (MBRs) have proven to be an extremely effective wastewater treatment process combining ultrafiltration with biological processes to produce high-quality effluent. However, one of the major drawbacks to this technology is membrane fouling – an inevitable process that reduces permeate production and increases operating costs. The prediction of membrane fouling in MBRs is important because it can provide decision support to wastewater treatment plant (WWTP) operators. Currently, mechanistic models are often used to estimate transmembrane pressure (TMP), which is an indicator of membrane fouling, but their performance is not always satisfactory. In this research, existing mechanistic and data-driven models used for membrane fouling are investigated. Data-driven machine learning techniques consisting of random forest (RF), artificial neural network (ANN), and long-short term memory network (LSTM) are used to build models to predict transmembrane pressure (TMP) at various stages of the MBR production cycle. The models are built with 4 years of high-resolution data from a confidential full-scale municipal WWTP. The model performances are examined using statistical measures such as coefficient of determination (R2), root mean squared error, mean absolute percentage error, and mean squared error. The results show that all models provide reliable predictions while the RF models have the best predictive accuracy when compared to the ANN and LSTM models. The corresponding R2 values for RF when predicting before, during, and after back pulse TMP are 0.996, 0.927, and 0.996, respectively. Model uncertainty (including hyperparameter and algorithm uncertainty) is quantified to determine the impact of hyperparameter tuning and the variance of extreme predictions caused by algorithm choice. The ANN models are most impacted by hyperparameter tuning and have the highest variability when predicting extreme values within each model’s respective hyperparameter range. The proposed models can be useful tools in providing decision support to WWTP operators employing fouling mitigation strategies, which can potentially lead to better operation of WWTPs and reduced costs. / Thesis / Master of Applied Science (MASc)

No description available.

Degradable low-fouling hydrogels are ideal vehicles for drug and cell delivery. For each application, hydrogel degradation rate must be re-optimized for maximum therapeutic benefit. We developed a method to rapidly tune degradation rates of low-fouling poly(oligo(ethylene glycol) methyl ether methacrylate) (P(EG)xMA) hydrogels by modifying two interdependent variables: (1) base-catalyzed crosslink degradation kinetics, dependent on crosslinker electronics (electron withdrawing groups (EWGs)); and (2) polymer hydration, dependent on the molecular weight (MW) of poly(ethylene glycol) (PEG) pendant groups. By controlling EWG strength and PEG pendant group MW, P(EG)xMA hydrogels were tuned to degrade over 6 to 52 d. A six-member P(EG)xMA copolymer library yielded slow and fast degrading low-fouling hydrogels for short- and long-term delivery applications. The degradation mechanism was also applied to RGD-functionalized poly(carboxybetaine methacrylamide) (PCBMAA) hydrogels to achieve slow (52 d) and fast (13 d) degrading low-fouling, bioactive hydrogels. / Thesis / Master of Science (MSc) / The delivery of drugs and cells to disease sites is hindered by transport barriers, which can be overcome through local delivery. Injectable hydrogels can serve as local depots that release drugs or cells to improve therapeutic benefit. Currently, however, hydrogels suffer from uncontrolled degradation in the body, degrading at unpredictable rates dependent on the local environment; hydrogels with predictable and tunable degradation rates are therefore required. Herein, we report a method to produce a library of polymers that in situ crosslink to form hydrogels with a range of degradation rates only influenced by the local environments pH, a known quantity. Moreover, the polymers are low-fouling and therefore have minimal non-specific interactions with biomolecules and cells, which improves biocompatibility.

Superhydrophobic (SHS) and lubricant-infused surfaces (LIS) exhibit exceptional non-wetting characteristics that make them attractive for energy production applications including steam condensation and fouling mitigation. The dissertation work focuses on application of non-wetting surfaces to energy production using a systematic approach examining each component of surface fabrication in three functional areas. First, SHS and LIS are fabricated using robust, scalable methods and tested for durability in heated, wet conditions and under high-energy water jet impingement. Clear performance differences are shown based on surface texturing, functionalizing agent, and infused lubricant. Second, SHS and LIS are applied to tube exteriors and evaluated for their ability to produce sustained dropwise condensation in a typical power plant condenser environment. The surfaces are shown to produce heat transfer coefficients up to 7-10 times that of film-wise condensation, with condenser effectiveness of 0.92 or better compared to effectiveness of about 0.6 in conventional condensers. Third, LIS on the interior of tubes are assessed in accelerated mineral fouling conditions. LIS are shown to mitigate calcium sulfate and calcium carbonate fouling under laminar conditions. The results of the study bear profound benefits to reducing the levelized cost of condensers and water uptake in thermoelectric power plants, that currently consume about 50% of the total water use in the U.S. / Doctor of Philosophy / Creating durable, hybrid surfaces for improved steam condensation and fouling mitigation would provide substantial impact to power generation worldwide. Bioinspired, non-wetting surfaces, such as superhydrophobic (SHS) and lubricant-infused surfaces (LIS) exhibit exceptional non-wetting characteristics that make them attractive for energy applications. Each of these non-wetting technologies, however, faces durability and scalability challenges that make them unfeasible for widespread, practical adoption. As a result, decades of materials science research have stagnated in the research laboratories with limited demonstrations of dropwise condensation and fouling mitigation in static situations. The dissertation work focuses on application of SHS and LIS to energy production using a systematic approach examining each component of surface fabrication in three functional areas. First, SHS and LIS are fabricated using robust, scalable methods and tested for durability using ASTM standard static and dynamic evaluation methods. Clear performance differences are shown based on surface texturing, functionalizing agent, and infused lubricant. Second, dropwise steam condensation on the surfaces are shown to exhibit heat transfer performance an order of magnitude greater than film-wise condensation in a typical power plant condenser environment. The surfaces are shown to produce heat transfer coefficients up to 7-10 times that of film-wise condensation, with condenser effectiveness of 0.92 or better compared to effectiveness of about 0.6 in conventional condensers. This work presents for the first time, a non-dimensional correlation for a priori prediction of LIS heat transfer performance given known qualities of the LIS. Third, challenges of fouling mitigation in power plants have been studied for over a decade. This work demonstrates for the first time that LIS applied to the interior of tubes mitigate calcium sulfate and calcium carbonate fouling in both static and laminar flow conditions.

Nanofiltration (NF) is an attractive option for the treatment of wastewater e.g. municipal wastewater and landfill leachate. However, membrane fouling can be a major obstacle in the implementation of this technology. Fouling of nanofiltration membranes by hu-mic acids (HA) was investigated using bisphenol A (BPA) as an indicator chemical to dif-ferentiate between various mechanisms that may lead to a change in solute rejection. Three commercially available NF membranes were investigated and an accelerated foul-ing condition was achieved with a foulant mixture containing humic acids in an electro-lyte matrix. The effects of membrane fouling on the rejection of BPA were interpreted with respect to the membrane pore sizes and the fouling characteristics. Results report-ed here indicate that calcium concentration in the feed solution could be a major factor governing the humic acid fouling process. Moreover, a critical concentration of calcium in the feed solution was observed, at which membrane fouling was most severe. Mem-brane fouling characteristics were observed by their influence on BPA rejection. Such influence could result in either an increase or decrease in rejection of BPA by the three different membranes depending on the rejection mechanisms involved. It is hypothe-sised that these mechanisms could occur simultaneously and that the effects of each might not be easily distinguished. However, it was observed that their relative contribu-tion was largely dependent upon membrane pore size. Pore blocking, which resulted in a considerable improvement in rejection, was prominent for the more open pore size TFC-SR2 membrane. In contrast, the cake-enhanced concentration polarisation (CECP) effect was more severe for the tighter NF270 and NF90 membranes. For hydrophobic solutes such as BPA, the formation of the fouling layer could also interfere with the so-lute-membrane interaction, and therefore, exert considerable influence on the separa-tion process. The combined impact of humic acid fouling and CaCO3 scaling on the rejection of trace organic contaminants by a commercially available nanofiltration membrane was inves-tigated in this study. Due to the presence of humic acid in the feed solution, CaCO3 scal-ing behaviour differed substantially from that of a pure CaCO3 solution. A prolonged induction period was consistently observed prior to the onset of membrane scaling. In addition, membrane scaling following humic acid fouling did not result in a complete loss of permeate flux. This is consistent with the absence of any large CaCO3 crystals. In fact, the CaCO3 crystals on the membrane surface were quite small and similar in size, which would result in a relatively porous cake layer. At the onset of CaCO3 scaling the rejection of all three trace organic contaminants started to decrease dramatically. The observed decrease in rejection of the trace organic contaminants was much more se-vere than that reported previously with a single layer of either organic or colloidal foul-ing. Such severe decrease in rejection can be attributed to the extended cake-enhanced concentration polarisation effect occurring as a result of the combination of membrane fouling and scaling. The porous CaCO3 scaling layer could lead to a substantial cake-enhanced concentration polarisation effect. In addition, the top CaCO3 scaling layer could reduce the wall shear rate within the underlying humic acid fouling layer, causing an additional concentration polarisation (CP) effect.:1 INTRODUCTION 1 1.1 Fundamentals of NF/RO 1 1.1.1 Solute transport through NF/RO membranes 2 1.1.2 Separation mechanisms 3 1.1.2.1 Steric size exclusion 3 1.1.2.2 Donnan effect 3 1.1.2.3 Electrostatic repulsion 4 1.1.2.4 Adsorption 4 1.1.3 Environmental applications of NF/RO 5 1.1.4 Drinking water treatment from groundwater and surface water sources 5 1.1.5 Water/Wastewater reclamation 7 1.2 Classification and materials of NF/RO membranes 7 1.2.1 Membrane classes 7 1.2.2 Membrane materials 8 1.2.3 Organic membrane materials 9 1.2.3.1 Polyamide membranes 9 1.2.3.2 Cellulose acetate membranes 9 1.2.4 Inorganic membrane materials 10 1.3 Removal of trace organic contaminants 11 1.3.1 Impact of membrane characteristics 14 1.3.1.1 Molecular weight cut-off/pore size 14 1.3.1.2 Surface charge 14 1.3.1.3 Hydrophobicity/hydrophilicity 15 1.3.1.4 Surface morphology 15 1.3.2 Impact of feed characteristics 17 1.3.2.1 pH value 17 1.3.2.2 Ionic strength 18 1.3.2.3 Organic matter 19 1.3.2.4 Presence of divalent ions 20 1.3.2.5 Presence of foulants 20 1.3.2.6 Temperature 20 1.3.3 Impact of solute characteristics 22 1.3.3.1 Molecular weight 22 1.3.3.2 Molecular size (length and width)/molecular volume 22 1.3.3.3 Minimum projection area/Equivalent width 23 1.3.3.4 Charge 23 1.3.3.5 Hydrophobicity/hydrophilicity 24 1.3.4 Impact of operational characteristics 25 1.3.4.1 Transmembrane pressure/permeate or transmembrane flux 25 1.3.4.2 Cross-flow velocity/recovery/concentration polarisation 25 1.3.5 Impact of fouling on rejection 26 1.3.5.1 Organic fouling 28 1.3.5.2 Colloidal fouling 30 1.3.5.3 Inorganic fouling (scaling) 31 1.3.5.4 Biological fouling 32 1.3.6 Impact of membrane cleaning on rejection 32 1.3.6.1 Changes of membrane morphology due to cleaning 32 1.3.6.2 Impact on rejection of TrOCs due to cleaning 33 1.3.7 Validation at pilot and full scale systems 35 2 MEMBRANE FOULING IN THE NANOFILTRATION OF LANDFILL LEACHATE AND ITS IMPACT ON TRACE CONTAMINANT REMOVAL 37 2.1 Introduction 37 2.2 Materials and Methods 40 2.2.1 Analytical reagents and chemicals 40 2.2.2 Nanofiltration membrane 40 2.2.3 Membrane filtration set-up and protocol 41 2.2.4 Analytical technique 42 2.3 Results and discussion 42 2.3.1 Landfill leachate characterisation 42 2.3.2 Physico-chemical properties of bisphenol A 43 2.3.3 Influence of the calcium concentration on the flux 44 2.3.4 Influence of fouling on the rejection of organic contaminants 46 2.4 Conclusions 48 3 CHARACTERISING HUMIC ACID FOULING OF NANOFILTRATION MEMBRANES USING BISPHENOL A AS A MOLECULAR INDICATOR 50 3.1 Introduction 50 3.2 Materials and methods 52 3.2.1 Model NF membranes and membrane characterisation 52 3.2.2 Model trace organic contaminant 52 3.2.3 Organic foulant 53 3.2.4 Membrane filtration set-up 54 3.2.5 Filtration protocol 55 3.2.6 Analytical technique 56 3.3 Results and discussions 56 3.3.1 Membrane characteristics 56 3.3.2 Membrane fouling behaviour 58 3.3.3 Change of membrane hydrophobicity 61 3.3.4 Effects of organic fouling on the nanofiltration of BPA 63 3.3.5 Effects of organic fouling on rejection: the mechanisms 65 3.4 Conclusions 67 4 EFFECTS OF FOULING AND SCALING ON THE REJECTION OF TRACE ORGANIC CONTAMINANTS BY A NANOFILTRATION MEMBRANE: THE ROLE OF CAKE-ENHANCED CONCENTRATION POLARISATION 69 4.1 Introduction 69 4.2 Materials and methods 71 4.2.1 Nanofiltration membrane 71 4.2.2 Chemicals and reagents 71 4.2.3 Crossflow membrane filtration system 72 4.2.4 Experimental protocol 73 4.2.5 SEM-EDS analysis 74 4.2.6 Analytical methods 75 4.3 Results and discussion 75 4.3.1 Membrane characteristics 75 4.3.2 Membrane fouling and scaling development 76 4.3.3 Effects of fouling/scaling on the membrane rejection behaviour 79 4.3.4 Cake-enhanced concentration polarisation 85 4.4 Conclusions 87 5 SUMMARY AND CONCLUSIONS 88 6 REFERENCES 94 7 ACKNOWLEDGEMENTS 112

Doctor of Philosophy / Department of Biological & Agricultural Engineering / Naiqian Zhang / Suspended sediment concentration (SSC) in water is one of the most important parameters to evaluate water quality. Monitoring SSC provides important information on determining sediment transport for soil erosion research and soil/water conservation practices. Sediment mass transported at a given time can be assessed by simultaneous SSC and water flow velocity measurements. Fouling, including bio-fouling, has damaging impact on optical SSC measurements over the long term. In this study, an inexpensive, real-time, self-cleaning, optical sediment and flow velocity sensor was developed. Laboratory experiments were conducted on a previously designed SSC sensor. A light modulation algorithm was designed to reduce the influence of ambient light, especially sunlight, on measurement accuracy. Statistical models to predict SSC based on measured light intensities were established and compared with neural network models. The statistical analysis showed that soil texture played an important role in SSC measurement accuracy while the designed sensor was capable of reducing the effect of water color on sensor performance. Neural-network models can further remove the influence of soil texture type on SSC measurement. The sensor design was simplified based on a stepwise selection analysis. Long-term field experiments were conducted in Kansas and Georgia to evaluate the sensor performance, the effect of fouling, including bio-fouling, on sensor lenses, and the effect of temperature on the measurement. Methods of removing the fouling effect through data correction were developed. Results indicated that the designed optical SSC sensor was capable of providing rapid response to SSC fluctuations in water flow. Temperature of the water body has an insignificant impact on SSC measurement. In order to reduce fouling, an air-blast cleaning mechanism was integrated into the optical sediment sensor. Laboratory experiments in a manually created fouling environment were conducted to observe the fouling process on sensor cases made of different materials, and to verify the effectiveness of air-blast cleaning in reducing fouling. Results indicated that air-blast cleaning mechanism was capable of reducing clay/silt fouling on sensor signals. The duration and frequency of air-blast cleaning can be determined and adjusted depending on actual field conditions. An air pressure drop test was conducted on the hose carrying pressurized air. Results showed negligible pressure drop.A flow velocity measurement function based on the cross-correlation principle was integrated into the optical sediment sensor. An experiment was conducted in laboratory to examine the sensor performance on velocity measurement using a closed circulation system. A solution of blue colorant, Brilliant Blue FCF, was used as an artificial source to absorb light emitted by LEDs in the sensor and the signal variation patterns were measured. The results indicated that the cross-correlation-based velocity sensor was capable of measuring water flow velocity within in a certain velocity range using the dye injection method.

<p>Biological invasions are an important issue of global change and an increased understanding of invasion processes is of crucial importance for both conservation managers and international trade. In this thesis, I have studied the invasion of the brown seaweed <i>Fucus evanescens</i>, to investigate the fate and effect of a perennial, habitat-forming seaweed introduced to a coastal ecosystem. A long-term study of the spread of <i>F. evanescens</i> in Öresund (southern Sweden) showed that the species was able to expand its range quickly during the first 20 years after the introduction, but that the expansion has been slow during the subsequent 30 years. Both in Öresund and in Skagerrak, the species is largely restricted to sites where native fucoids are scarce. Laboratory experiments showed that the restricted spread of <i>F. evanescens</i> cannot be explained by the investigated abiotic factors (wave exposure and salinity), although salinity restricts the species from spreading into the Baltic Sea. Neither did I find evidence for that herbivores or epibiota provide biotic resistance to the invader. On the contrary, <i>F. evanescens</i> was less consumed by native herbivores, both compared to the native fucoids and to <i>F. evanescens</i> populations in its native range, and little overgrown by epiphytes. Instead, the restricted spread may be due to competition from native seaweeds, probably by pre-occupation of space, and the establishment has probably been facilitated by disturbance. </p><p>The studies provided little support for a general enemy release in introduced seaweeds. The low herbivore consumption of <i>F. evanescens</i> in Sweden could not be explained by release from specialist herbivores. Instead, high levels of chemical anti-herbivore defence metabolites (phlorotannins) could explain the pattern of herbivore preference for different fucoids. Likewise, the low epibiotic colonisation of <i>F. evanescens </i>plants could be explained by high resistance to epibiotic survival. This shows that colonisation of invading seaweeds by native herbivores and epibionts depends on properties of the invading species. The large differences between fucoid species in their quality as food and habitat for epibionts and herbivores imply that invasions of such habitat-forming species may have a considerable effect on a number of other species in shallow coastal areas. However, since <i>F. evanescens</i> did not exclude other fucoids in its new range, its effect on the recipient biota is probably small.</p>