Distinct Antifouling Mechanisms on Different Chain Densities of Zwitterionic Polymers.

Antifouling polymer coating surfaces are used in widespread industries applications. Zwitterionic polymers have been identified as promising materials in developing polymer coating surfaces. Importantly, the density of the polymer chains is crucial for acquiring superior antifouling performance. This study introduces two different zwitterionic polymer density surfaces by applying molecular modeling tools. To assess the antifouling performance, we mimic static adsorption test, by placing the foulant model bovine serum albumin (BSA) on the surfaces. Our findings show that not only the density of the polymer chain affect antifouling performance, but also the initial orientation of the BSA on the surface. Moreover, at a high-density surface, the foulant either detaches from the surface or anchor on the surface. At low-density surface, the foulant does not detach from the surface, but either penetrates or anchors on the surface. The anchoring and the penetrating mechanisms are elucidated by the electrostatic interactions between the foulant and the surface. While the positively charged ammonium groups of the polymer play major role in the interactions with the negatively charged amino acids of the BSA, in the penetrating mechanism the ammonium groups play minor role in the interactions with the contact with the foulant. The sulfonate groups of the polymer pull the foulant in the penetrating mechanism. Our work supports the design of a high-density polymer chain surface coating to prevent fouling phenomenon. Our study provides for the first-time insights into the molecular mechanism by probing the interactions between BSA and the zwitterion surface, while testing high- and low-densities polymer chains.

Grafted Polymer Coatings Enhance Fouling Inhibition by an Antimicrobial Peptide on Reverse Osmosis Membranes.

Bacterial biofilms that are formed on surfaces are highly detrimental to many areas of industry and medicine. Seawater desalination by reverse osmosis (RO) suffers from biofilm growth on the membranes (biofouling), which limits its widespread use because biofouling decreases water permeance and necessitates module cleaning and replacement, leading to increased economic and environmental costs. Antimicrobial peptides (AMPs) bound covalently to RO membranes inhibit biofilm growth and might delay membrane biofouling. Here we examined how various hydrophilic membrane coatings composed of zwitterionic, neutral, positively charged, and poly(ethylene glycol) (PEG)-grafted polymers affected the biocidal activity and the biofilm inhibition of a covalently bonded AMP on RO membranes. AMP magainin-2 was linked by the copper-catalyzed azide-alkyne cycloaddition reaction to a series of RO membranes that were grafted with different methacrylate polymers. Surface characterization by infrared spectroscopy, X-ray photoelectron spectroscopy, and water drop contact angle gave evidence of successful RO modifications, and zeta potential analysis reflected the increase in surface charge due to the linked, positively charged peptide. All AMP-modified membranes inhibited Pseudomonas aeruginosa growth compared to unmodified membranes, and the grafted methacrylic polymers did not significantly interfere with the peptide activity. On the other hand, membranes coated with zwitterionic and other acrylate polymers including AMP attachment inhibited biofilm growth more than either the AMP or the polymer coating alone. This enhancement led to ∼20% less biofilm biovolume on the membrane surfaces. The combination of antimicrobial coatings with polymer coatings known to resist fouling might aid future designs of surface coatings susceptible to biofilm growth.

Surface-Induced Silica Scaling during Brackish Water Desalination: The Role of Surface Charge and Specific Chemical Groups.

Silica scaling of membranes used in reverse osmosis desalination processes is a severe problem, especially during the desalination of brackish groundwater due to high silica concentrations. This problem limits the water supply in inland arid and semiarid regions. Here, we investigated the influence of surface-exposed organic functional groups on silica precipitation and scaling. A test solution simulating the mineral content of brackish groundwater desalination brine at 75% recovery was used. The mass and chemical composition of the precipitated silica was monitored using a quartz crystal microbalance, X-ray photoelectron spectroscopy, and infrared spectroscopy, showing that surfaces with positively charged groups induced rapid silica precipitation, and the rate of silica precipitation followed the order -NH2 ∼ -N+(CH3)3 > -NH2/-COOH > -H2PO3 ∼ -OH > -COOH > -CH3. Force vs distance AFM measurements showed that the adhesion energy between a silica colloid glued to AFM cantilever and the studied surfaces increased as the surface charge changed from negative to positive. Thus, for the first time direct measurements of molecular forces and specific chemical groups that govern silica scaling during brackish water desalination is reported here. The influence of the different functional groups and the effect of the surface charge on silica precipitation that were found here can be used to design membranes that resist silica scaling in membrane-based desalination processes.

Synergy on Surfaces: Anti-Biofouling Interfaces Using Surface-Attached Antimicrobial Peptides PGLa and Magainin-2.

The synergistic effect of antimicrobial compounds is an important phenomenon that can increase the potency of treatment and might be useful against the formation of biofilms on surfaces. A strong inhibition of microbial viability on surfaces can potentially delay the development of biofilms on treated surfaces, thereby enhancing the performance of water-purification technologies and medical devices, for example, to prevent hospital-acquired infections. However, the synergistic effects of surface-immobilized antimicrobial peptides (AMPs) have not yet been reported. Here, we demonstrate the synergistic antimicrobial effects of the AMPs PGLa and magainin-2 on modified reverse-osmosis (RO) membranes. These AMPs are known to act synergistically in the free state, but their antimicrobial synergistic effects have not yet been reported in a surface-immobilized state. The AMPs were functionalized with alkyne linkers and covalently attached to RO membranes modified with azides, using a click chemistry reaction. The resulting RO membranes showed reduced contact angles, indicating increased wettability. X-ray photoelectron spectroscopy confirmed the presence of the two peptides on the membranes via changes in the amounts of carbon, oxygen, and sulfur, which led to an increased S/C ratio, probably because of the sulfur present in the methionine residue of the peptides. The synergistic activity was measured with the free peptides in solution and covalently bound on RO membrane surfaces by observing increased leakage of 5(6)-carboxyfluorescein from large unilamellar vesicles. The synergistic antimicrobial activity against Pseudomonas aeruginosa was observed using surface-activity assays, where the AMP-modified RO membranes showed an effective inhibition of P. aeruginosa biofilm growth, as compared with unmodified membranes. An enhanced activity of antimicrobials on surfaces might lead to potent antimicrobial surfaces, which could result in more fouling-resistant water-treatment membranes.

Saline Groundwater from Coastal Aquifers As a Source for Desalination.

Reverse osmosis (RO) seawater desalination is currently a widespread means of closing the gap between supply and demand for potable water in arid regions. Currently, one of the main setbacks of RO operation is fouling, which hinders membrane performance and induces pressure loss, thereby reducing system efficiency. An alternative water source is saline groundwater with salinity close to seawater, pumped from beach wells in coastal aquifers which penetrate beneath the freshwater-seawater interface. In this research, we studied the potential use of saline groundwater of the coastal aquifer as feedwater for desalination in comparison to seawater using fieldwork and laboratory approaches. The chemistry, microbiology and physical properties of saline groundwater were characterized and compared with seawater. Additionally, reverse osmosis desalination experiments in a cross-flow system were performed, evaluating the permeate flux, salt rejection and fouling propensities of the different water types. Our results indicated that saline groundwater was significantly favored over seawater as a feed source in terms of chemical composition, microorganism content, silt density, and fouling potential, and exhibited better desalination performance with less flux decline. Saline groundwater may be a better water source for desalination by RO due to lower fouling potential, and reduced pretreatment costs.

Humanin Derivatives Inhibit Necrotic Cell Death in Neurons.

Humanin and its derivatives are peptides known for their protective antiapoptotic effects against Alzheimer's disease. Herein, we identify a novel function of the humanin-derivative AGA(C8R)-HNG17 (namely, protection against cellular necrosis). Necrosis is one of the main modes of cell death, which was until recently considered an unmoderated process. However, recent findings suggest the opposite. We have found that AGA(C8R)-HNG17 confers protection against necrosis in the neuronal cell lines PC-12 and NSC-34, where necrosis is induced in a glucose-free medium by either chemohypoxia or by a shift from apoptosis to necrosis. Our studies in traumatic brain injury models in mice, where necrosis is the main mode of neuronal cell death, have shown that AGA(C8R)-HNG17 has a protective effect. This result is demonstrated by a decrease in a neuronal severity score and by a reduction in brain edema, as measured by magnetic resonance imaging (MRI). An insight into the peptide's antinecrotic mechanism was attained through measurements of cellular ATP levels in PC-12 cells under necrotic conditions, showing that the peptide mitigates a necrosis-associated decrease in ATP levels. Further, we demonstrate the peptide's direct enhancement of the activity of ATP synthase activity, isolated from rat-liver mitochondria, suggesting that AGA(C8R)-HNG17 targets the mitochondria and regulates cellular ATP levels. Thus, AGA(C8R)-HNG17 has potential use for the development of drug therapies for necrosis-related diseases, for example, traumatic brain injury, stroke, myocardial infarction, and other conditions for which no efficient drug-based treatment is currently available. Finally, this study provides new insight into the mechanisms underlying the antinecrotic mode of action of AGA(C8R)-HNG17.

Diminished swelling of cross-linked aromatic oligoamide surfaces revealing a new fouling mechanism of reverse-osmosis membranes.

Swelling of the active layer of reverse osmosis (RO) membranes has an important effect on permeate water flux. The effects of organic- and biofouling on the swelling of the RO membrane active layer and the consequent changes of permeate flux are examined here. A cross-linked aromatic oligoamide film that mimics the surface chemistry of an RO polyamide membrane was synthesized stepwise on gold-coated surfaces. Foulant adsorption to the oligoamide film and its swelling were measured with a quartz crystal microbalance, and the effects of fouling on the membrane's performance were evaluated. The foulants were extracellular polymeric substances (EPS) extracted from fouled RO membranes and organic compounds of ultrafiltration permeate (UFP) from a membrane bioreactor used to treat municipal wastewater. The adsorbed foulants affected the swelling of the cross-linked oligoamide film differently. EPS had little effect on the swelling of the oligoamide film, whereas UFP significantly impaired swelling. Permeate flux declined more rapidly under UFP fouling than it did under EPS. Foulant adsorption was shown to diminish swelling of the aromatic oligoamide surfaces. Among the already known RO membrane fouling mechanisms, a novel RO fouling mechanism is proposed, in which foulant-membrane interactions hinder membrane swelling and thus increase hydraulic resistance.

Nitrate removal from contaminated groundwater by micellar-enhanced ultrafiltration using a polyacrylonitrile membrane with a hydrogel-stabilized ZIF-L layer.

Contamination of groundwater by nitrate from intensive agriculture is a serious problem globally. Excessive fertilization has led to nitrate contamination of the Coastal Aquifer in Israel. Here we report the efficient removal of nitrate from contaminated groundwater by micellar-enhanced ultrafiltration (MEUF) using a specially tailored membrane. Graft polymerization with hydrophilic poly(methacrylate) and incorporation of porous zeolitic imidazole framework ZIF-L nanoparticles imparted antifouling properties to the membrane. The resulting modified membrane showed high water permeance (82.2 ± 1.7 L·m-2·h-1·bar-1). The efficiency of nitrate removal by MEUF was tested using cetylpyridinium chloride as a surfactant in nitrate-contaminated groundwater collected from the Coastal Aquifer of Israel. The membrane reduced nitrate levels from 40-70 to levels of 6.8-29.5 mg·L-1, depending on the groundwater composition; further reduction to 6.1-24.1 mg·L-1 with complete surfactant rejection was achieved via two-stage membrane filtration, which showed high permeate flux (between 32.1 ± 0.9 and 45.9 ± 0.6 L·m-2·h-1) at 2 bar. The membrane maintained stable separation performance during multiple cycles, and the flux recovery ratio was >93 %. Nitrate concentrations fell well below the acceptable limit for drinking water, allowing the treated water to be used without restriction. Overall, the membrane has the potential to allow efficient removal by MEUF of nitrate from contaminated groundwater.

Effects of biological molecules on calcium mineral formation associated with wastewater desalination as assessed using small-angle neutron scattering.

Calcium phosphate scale formation on reverse osmosis (RO) membranes is one of the main limitations on cost-effective desalination of domestic wastewater worldwide. It has been shown that organic agents affect mineralization. In this study, we explored mineralization in the presence of two biofilm-relevant organic compounds, the proteins bovine serum albumin (BSA) and lysozyme, in a simulated secondary effluent (SSE) solution using small-angle neutron scattering (SANS), and applied the results to analyses of mineral precipitation in RO desalination of secondary effluents of wastewater. The two proteins are prominent members of bacterial extracellular polymeric substances (EPSs), forming biofilms that are frequently associated with RO-membrane fouling during wastewater desalination. Laboratory experiments showed that both proteins in SSE solution are involved in complex mineralization processes. Only small portions of both protein fractions are involved in mineralization processes, whereas most of the protein fractions remain as monomers in solution. Contrast variation showed that composite particles of mineral and protein are formed instantaneously to a radius of gyration of about 300 Å, coexisting with particles of about µm size. After about one day, these large particles start to grow again at the expense of the 300 Å particles. The volume fraction of the 300 Å particles is of the order of 2 × 10(-4), which is too large to represent calcium phosphate such as hydroxyapatite as the only mineral present. Considering the data of mineral volume fraction obtained here as well as the solubility product of possible mineral polymorphs in the SSE solution, we suggest the formation of protein-mineral particles of hydroxyapatite and calcium carbonate during scale formation.

Chemical and physical factors in design of antibiofouling polymer coatings.

Because most "low fouling" polymers resisting bacterial attachment are hydrophilic, they are usually also significantly swollen. Swelling leads to purely physical dilution of interaction and weakens attachment; however, these nonspecific contributions are usually not separated from the specific effect of polymer chemistry. Taking advantage of the fact that chemistry and swelling of hydrogels may be independently varied through the fraction of a cross-linker, the roles of chemistry and physical dilution (swelling) in bacterial attachment are analyzed for selected hydrogels. Using as a quantitative indicator the rate of bacterial deposition in a parallel plate setup under defined flow conditions, the observed correlation of deposition rate with swelling provides a straightforward comparison of gels with different chemistries that can factor out the effect of swelling. In particular, it is found that chemistry appears to contribute similarly to bacterial deposition on hydrogels prepared from acrylamide and a zwitterioninic monomer 2-(methacryloyloxy)ethyl) dimethyl-(3-sulfopropyl) ammonium hydroxide so that the observed differences may be related to swelling only. In contrast, these gels were inferior to PEG-based hydrogels, even when swelling of the latter was lower, indicating a greater contribution of PEG chemistry to reduced bacterial deposition. This demonstrates that swelling must be accounted for when comparing different biofouling-resistant materials. Chemical and physical principles may be combined in hydrogel coatings to develop efficient antibiofouling surfaces.

Surface properties and reduced biofouling of graft-copolymers that possess oppositely charged groups.

Microbial biofilms and their components present a major obstacle for ensuring the long-term effectiveness of membrane processes. Graft polymerization on membrane surfaces, in general, and grafting with oppositely charged monomers, have been shown to reduce biofouling significantly. In this study, surface forces and macromolecular properties of graft copolymers that possess oppositely charged groups were related to their potent antibiofouling behavior. Graft polymerization was performed using the negatively charged 3-sulphopropyl methacrylate (SPM) and positively charged [2-(methacryloyloxy)ethyl]-trimethylammonium (MOETMA) monomers to yield a copolymer layer on polyvinylidene fluoride (PVDF) surface. Quartz crystal microbalance with dissipation monitoring (QCM-D) technology was used to monitor the reduced adsorption of extracellular polymeric substances (EPS) extracted from a membrane bioreactor (MBR) wastewater treatment facility. Complemented measurements of attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy provided evaluation of the antifouling properties of the surface. Increase in water content in grafted layer exposed to 100 mM aqueous NaCl solution was observed by QCM-D. Therefore, the grafted copolymer layer is swelled in the presence of 100 mM NaCl because of reversing of polymer self-association by counterions. Force measurements by atomic force microscopy (AFM) showed an increased repulsion between a carboxylate-modified latex (CML) particle probe and a modified PVDF surface, especially in the presence of 100 mM NaCl. The hydration and swelling of the grafted polymer layer are shown to repel EPS and reduce their adsorption. Delineating the surface properties of antifouling grafted layers may lead to the design of novel antifouling surfaces.

Studying the role of common membrane surface functionalities on adsorption and cleaning of organic foulants using QCM-D.

Adsorption of organic foulants on nanofiltration (NF) and reverse osmosis (RO) membrane surfaces strongly affects subsequent fouling behavior by modifying the membrane surface. In this study, impact on organic foulant adsorption of specific chemistries including those in commercial thin-film composite membranes was investigated using self-assembled monolayers with seven different ending chemical functionalities (-CH(3), -O-phenyl, -NH(2), ethylene-glycol, -COOH, -CONH(2), and -OH). Adsorption and cleaning of protein (bovine serum albumin) and polysaccharide (sodium alginate) model foulants in two solution conditions were measured using quartz crystal microbalance with dissipation monitoring, and were found to strongly depend on surface functionality. Alginate adsorption correlated with surface hydrophobicity as measured by water contact angle in air; however, adsorption of BSA on hydrophilic -COOH, -NH(2), and -CONH(2) surfaces was high and dominated by hydrogen bond formation and electrostatic attraction. Adsorption of both BSA and alginate was the fastest on -COOH, and adsorption on -NH(2) and -CONH(2) was difficult to remove by surfactant cleaning. BSA adsorption kinetics was shown to be markedly faster than that of alginate, suggesting its importance in the formation of the conditioning layer. Surface modification to render -OH or ethylene-glycol functionalities are expected to reduce membrane fouling.

Redox condition of saline groundwater from coastal aquifers influences reverse osmosis desalination process.

Reverse osmosis (RO) seawater desalination is a widely applied technological process to supply potable water worldwide. Recently, saline groundwater (SGW) pumped from beach wells in coastal aquifers that penetrate beneath the freshwater-seawater interface is considered as a better alternative water source to RO seawater desalination as it is naturally filtered within the sediments which reduces membrane fouling and pre-treatment costs. The SGW of many coastal aquifers is anoxic - and thus, in a low redox stage - has elevated concentrations of dissolved manganese, iron and sulfides. We studied the influence of the SGW redox stage and chemistry on the performance - permeate flux and fouling properties - of RO desalination process. SGWs from three different coastal aquifers were sampled and characterized chemically, and RO desalination experiments were performed under inert and oxidized conditions. Our results show that all three aquifers have anoxic saline groundwater and two of them have intensive anaerobic oxidation of organic matter. Two aquifers were found to be in the denitrification stage or slightly lower and the third one in the sulfate reduction stage. Our results indicate that the natural redox stage of SGWs from coastal aquifers affects the performance of RO desalination. All SGW types showed better RO performance over seawater desalination. Furthermore, air oxidation of the SGW was accompanied with pH elevation, which increased the membrane fouling. Hence, keeping the feed water unexposed to atmospheric conditions for maintaining the natural reducing stage of the SGW is crucial for low fouling potential. The observed benefits of using naturally reduced SGW in RO desalination have significant implications for reduction in overall process costs.

Silica Fouling in Reverse Osmosis Systems-Operando Small-Angle Neutron Scattering Studies.

We present operando small-angle neutron scattering (SANS) experiments on silica fouling at two reverse osmose (RO) membranes under almost realistic conditions of practiced RO desalination technique. To its realization, two cells were designed for pressure fields and tangential feed cross-flows up to 50 bar and 36 L/h, one cell equipped with the membrane and the other one as an empty cell to measure the feed solution in parallel far from the membrane. We studied several aqueous silica dispersions combining the parameters of colloidal radius, volume fraction, and ionic strength. A relevant result is the observation of Bragg diffraction as part of the SANS scattering pattern, representing a crystalline cake layer of simple cubic lattice structure. Other relevant parameters are silica colloidal size and volume fraction far from and above the membrane, as well as the lattice parameter of the silica cake layer, its volume fraction, thickness, and porosity in comparison with the corresponding permeate flux. The experiments show that the formation of cake layer depends to a large extent on colloidal size, ionic strength and cross-flow. Cake layer formation proved to be a reversible process, which could be dissolved at larger cross-flow. Only in one case we observed an irreversible cake layer formation showing the characteristics of an unstable phase transition. We likewise observed enhanced silica concentration and/or cake formation above the membrane, giving indication of a first order liquid-solid phase transformation.

Glycidyl and Methyl Methacrylate UV-Grafted PDMS Membrane Modification toward Tramadol Membrane Selectivity.

Pharmaceutical wastewater pollution has reached an alarming stage, as many studies have reported. Membrane separation has shown great performance in wastewater treatment, but there are some drawbacks and undesired byproducts of this process. Selective membranes could be used for pollutant investigation sensors or even for pollutant recovery. The polydimethylsiloxane (PDMS) membrane was first tested on separated and mixed antibiotic (ATB) water solutions containing sulfamethoxazole (SM), trimethoprim (TMP), and tetracycline (TET). Then, the bare and ultra-violet grafted (UV-grafted) PDMS membranes (MMA-DMAEMA 10, GMA-DMAEMA 5, and GMA-DMAEMA 10) were tested in tramadol (TRA) separation, where the diffusion coefficient was evaluated. Finally, the membranes were tested in pertraction with a mixture of SM, TMP, TET, and TRA. The membranes were characterized using the following methods: contact angle measurement, FTIR, SEM/EDX, and surface and pore analysis. The main findings were that TET was co-eluted during mixed ATB pertraction, and GMA-DMAEMA 5 was found to selectively permeate TRA over the present ATBs.

Modified Single-Walled Carbon Nanotube Membranes for the Elimination of Antibiotics from Water.

The hydrophilic and hydrophobic single-walled carbon nanotube membranes were prepared and progressively applied in sorption, filtration, and pertraction experiments with the aim of eliminating three antibiotics-tetracycline, sulfamethoxazole, and trimethoprim-as a single pollutant or as a mixture. The addition of SiO2 to the single-walled carbon nanotubes allowed a transparent study of the influence of porosity on the separation processes. The mild oxidation, increasing hydrophilicity, and reactivity of the single-walled carbon nanotube membranes with the pollutants were suitable for the filtration and sorption process, while non-oxidized materials with a hydrophobic layer were more appropriate for pertraction. The total pore volume increased with an increasing amount of SiO2 (from 743 to 1218 mm3/g) in the hydrophilic membranes. The hydrophobic layer completely covered the carbon nanotubes and SiO2 nanoparticles and provided significantly different membrane surface interactions with the antibiotics. Single-walled carbon nanotubes adsorbed the initial amount of antibiotics in less than 5 h. A time of 2.3 s was sufficient for the filtration of 98.8% of sulfamethoxazole, 95.5% of trimethoprim, and 87.0% of tetracycline. The thicker membranes demonstrate a higher adsorption capacity. However, the pertraction was slower than filtration, leading to total elimination of antibiotics (e.g., 3 days for tetracycline). The diffusion coefficient of the antibiotics varies between 0.7-2.7 × 10-10, depending on the addition of SiO2 in perfect agreement with the findings of the textural analysis and scanning electron microscopy observations. Similar to filtration, tetracycline is retained by the membranes more than sulfamethoxazole and trimethoprim.

Effect of surface-exposed chemical groups on calcium-phosphate mineralization in water-treatment systems.

Calcium-phosphate-scale formation on reverse osmosis (RO) membranes is a major limiting factor for cost-effective desalination of wastewater. We determined the effects of various organic chemical groups found on membrane surfaces on calcium-phosphate scaling. Langmuir films exposing different functional groups were equilibrated with a solution simulating the ionic profile of secondary effluent (SSE). Surface pressure-area (Langmuir) isotherms combined with ICP elemental analyses of the interfacial precipitate suggested acceleration of calcium-phosphate mineralization by the surface functional groups in the order: PO(4) > COOH ∼ NH(2) > COOH:NH(2) (1:1) > OH > ethylene glycol. Immersion of gold-coated silicon wafers self-assembled with different alkanethiols in SSE solution showed formation of a hydroxyapatite precipitate by X-ray diffraction and ATR-IR analysis. Data showed diverse influences of functional groups on mineralization, implying low calcium-phosphate scaling for uncharged surfaces or surfaces coated with both positively and negatively charged groups. This information is valuable for understanding scaling processes, and for designing of novel low-scaling membranes for water desalination.

The effects of long-term saline groundwater pumping for desalination on the fresh-saline water interface: Field observations and numerical modeling.

This study tests for the first time the long-term effects of pumping saline groundwater (SGW) as feed for a desalination plant on a coastal aquifer. Field measurements combined with 3D modeling of the hydrological conditions were conducted to examine the effects of SGW pumping on the aquifer system. The plant is next to the city of Almeria (South East Spain) and has been operating since 2006. It uses multiple beach wells along the shore to draw SGW from beneath the fresh-saline water interface (FSI) of the Andarax coastal aquifer. The long-term impact of the intensive pumping on the aquifer was assessed by electrical conductivity profiles in three observation wells during 12 years of pumping. The FSI deepened with continuous pumping, reaching a decrease of ~50 m in the observation well closest to the pumping wells. A calibrated three-dimensional numerical model of the Andarax aquifer replicates the freshening of the aquifer due to the continuous pumping, resulting in a salinity decrease of ~16% in the vicinity of the wells. The salinity decrease stabilizes at 17%, and the model predicts no further significant decrease in salinity for additional 20 years. Submarine groundwater discharge is lowered due to the SGW pumping and ~19,000,000 m3 of freshwater has not lost to the sea during the 12 years of pumping with a rate of ~1,100,000 m3 yr-1 after 6 years of pumping. After pumping cessation, hydrostatic equilibrium would take about 20 years to recover. This work presents the complex dynamics of the FSI due to the SGW pumping for desalination in the first real long-term scenario. It shows by combining field work and numerical modeling, a significant freshening of the aquifer by pumping SGW, emphasizing an additional advantage and the effectiveness of this use as a negative hydraulic barrier against seawater intrusion.

Morphology of Thin Film Composite Membranes Explored by Small-Angle Neutron Scattering and Positron-Annihilation Lifetime Spectroscopy.

The morphology of thin film composite (TFC) membranes used in reverse osmosis (RO) and nanofiltration (NF) water treatment was explored with small-angle neutron scattering (SANS) and positron-annihilation lifetime spectroscopy (PALS). The combination of both methods allowed the characterization of the bulk porous structure from a few Å to µm in radius. PALS shows pores of 4.5 Å average radius in a surface layer of about 4 m thickness, which become 40% smaller at the free surface of the membranes. This observation may correlate with the glass state of the involved polymer. Pores of similar size appear in SANS as closely packed pores of 6 Å radius distributed with an average distance of 30 Å. The main effort of SANS was the characterization of the morphology of the porous polysulfone support layer as well as the fibers of the nonwoven fabric layer. Contrast variation using the media H2O/D2O and supercritical CO2 and CD4 identified the polymers of the support layers as well as internal heterogeneities.

The effect of pumping saline groundwater for desalination on the fresh-saline water interface dynamics.

Over the past few decades, seawater desalination has become a necessity for freshwater supply in many countries worldwide, particularly in arid and semi-arid regions. One potentially high-quality feed water for desalination is saline groundwater (SGW) from coastal aquifers, which has lower fouling propensity than seawater. This study examines the effect of pumping SGW from a phreatic coastal aquifer on fresh groundwater, particularly on the dynamics of the fresh-saline water interface (FSI). Initially, we constructed a 3D finite-element model of a phreatic coastal aquifer by using the FEFLOW software, which solves the coupled variable density groundwater flow and solute transport equations. Then, we compared and validated the results of the model to those of a field-scale pumping test. The model indicates that pumping SGW from a coastal aquifer freshens the aquifer and rehabilitates parts that were salinized due to seawater intrusion - an effect that increases with increasing pumping rate. In addition, when simultaneously pumping fresh groundwater further inland and SGW from below the FSI, the freshening effect is less pronounced and the salinity of the aquifer is more stable. In line with the results of the model, the field experiment revealed that salinity in the observation well decreases over the course of pumping. Taken together, our findings demonstrate that, in addition to providing a high-quality source feed water for desalination, pumping SGW does not salinize the aquifer and even rehabilitates it by negating the effect of seawater intrusion. These findings are important for planning shoreline desalination facilities and for managing arid coastal regions with lack of water supply and over exploited aquifers.