Semi-Continuous Desalination and Concentration of Small-Volume Samples.

Electrodialysis is an electric-field-mediated process separating ions exploiting selective properties of ion-exchange membranes. The ion-exchange membranes create an ion-depleted zone in an electrolyte solution adjacent to the membrane under DC polarization. We constructed a microfluidic system that uses the ion-depleted zone to separate ions from the processed water solution. We tested the separation performance by desalting a model KCl solution spiked with fluorescein for direct observation. We showed both visually and by measuring the conductivity of the output solutions that the system can work in three modes of operation referred to as continuous desalination, desalination by accumulation, and unsuccessful desalination. The mode of operation can easily be set by changing the control parameters. The desalination factors for the model KCl solution reached values from 80 to 100%, depending on the mode of operation. The concentration factor, given as a ratio of concentrate-to-feed concentrations, reached zero for desalination by accumulation when only diluate was produced. The water recovery, therefore, was infinite at these conditions. Independent control of the diluate and concentrate flow rates and the DC voltage turned our system into a versatile platform, enabling us to set proper conditions to process various samples.

Artificial Water Channels: Towards Biomimetic Membranes for Desalination.

Natural Aquaporin (AQP) channels are efficient water translocating proteins, rejecting ions. Inspired by this masterpiece of nature, Artificial Water Channels (AWCs) with controlled functional structures, can be potentially used to mimic the AQPs to a certain extent, offering flexible avenues toward biomimetic membranes for water purification. The objective of this paper is to trace the historical development and significant advancements of current reported AWCs. Meanwhile, we attempt to reveal important structural insights and supramolecular self-assembly principles governing the selective water transport mechanisms, toward innovative AWC-based biomimetic membranes for desalination.

Resistance of a Halobacterium salinarum isolate from a solar saltern to cadmium, lead, nickel, zinc, and copper.

The current study focuses on the tolerance of a strain of Halobacterium salinarum isolated from Sfax solar saltern (Tunisia) towards cadmium (Cd), lead (Pb), nickel (Ni), zinc (Zn), and copper (Cu) by using agar dilution methods in complex and minimal media. The results showed the least inhibitory metals based on Minimum Inhibitory Concentrations (MICs) were lead (MIC = 4.5 mM), cadmium (MIC = 4 mM), and nickel (MIC = 2.5 mM) in complex medium. The MICs of these metals were more inhibitory (MIC < 2 mM) in the other tested media. The archaeal strain revealed a high sensitivity for copper and zinc, with MICs below 0.5 mM for both metals. Growth kinetics in complex and minimal media showed the strain to be more sensitive to the metals in liquid media than in solid media. The growth kinetic assays indicated the presence of selected heavy metals resulted in a lower growth rate and lower total cell mass relative to the control. Despite that cadmium and lead are nonessential and have no nutrient value, they were the most tolerated metals by H. salinarum strain. In addition, pigment intensity in the strain was inhibited by the presence of the heavy metals relative to the control.

Microfluidic Microwave Sensor for Detecting Saline in Biological Range.

A device for measuring biological small volume liquid samples in real time is appealing. One way to achieve this is by using a microwave sensor based on reflection measurement. A prototype sensor was manufactured from low cost printed circuit board (PCB) combined with a microfluidic channel made of polymethylsiloxane (PDMS). Such a sensor was simulated, manufactured, and tested including a vacuum powered sample delivery system with robust fluidic ports. The sensor had a broad frequency band from 150 kHz to 6 GHz with three resonance frequencies applied in sensing. As a proof of concept, the sensor was able to detect a NaCl content of 125 to 155 mmol in water, which is the typical concentration in healthy human blood plasma.

Performance and autopsy of nanofiltration membranes at an oil-field wastewater desalination plant.

In this study, the long-term operational performance of an on-site NF facility at a full-scale oil-field wastewater desalination plant was monitored. The NF facility with poor permeability due to membrane fouling enables efficient multivalent salt removal (rejections of Mg2+, Ca2+, Fe3+, and Al3+ were approximately 100%). Moreover, a comparison of the cleaning efficiencies of two on-site cleaning modes indicated that PL-007 cleaning helped to improve the effectiveness of subsequent acid cleaning in the removal of inorganic foulants. Furthermore, a spiral-wound NF membrane module harvested from the plant was unfolded and autopsied. The results showed that both anionic polyacrylamide (APAM) and crude oil were identified as the predominant organic matter on the membrane surface and collectively accounted for a substantial fraction (86.3%) in terms of dry weight. Additionally, dissolved organics with a high molecular weight were prone to accumulation on the membrane surface. Multivalent elements, including Mg, Ca, Al, Fe, and Si, were the primary inorganic species in the fouling layer. Among the inorganic elements, Si occupied a high proportion and existed in the form of SiO2 in the fouling layer. According to the autopsy results, organic fouling combined with inorganics was responsible for the decline in the flux.

Conformal and Disposable Antenna-Based Sensor for Non-Invasive Sweat Monitoring.

This paper presents a feasibility study for a non-wearable, conformal, low cost, and disposable antenna-based sensor for non-invasive hydration monitoring using sweat. It is composed of a patch antenna implemented on a cellulose filter paper substrate and operating in the range 2⁻4 GHz. The paper substrate can absorb liquids, such as sweat on the skin, through two slots incorporated within the antenna structure. Thus, the substrate dielectric properties are altered according to the properties of the absorbed liquid. Changes in reflection-based measurements are used to analyze salt solutions and artificial sweat, specifically the amount of sampled solution and the sodium chloride (NaCl) concentration. Using the shift in resonant frequency and magnitude of the reflection coefficient, NaCl concentrations in the range of 8.5⁻200 mmol/L, representing different hydration states, are detected. The measurements demonstrate the feasibility of using microwave based measurements for hydration monitoring using sweat.

Highly Efficient Desalting by Silica Isoporous Membrane-Based Microfluidic Chip for Electrospray Ionization Mass Spectrometry.

Nonvolatile buffers and inorganic salts used for isolation and stabilization of biological samples are essential to be cleaned up prior to mass spectrometry (MS) analysis because of their deleterious effects such as ion suppression and instrumental pollution. In this work, a centimeter-scale continuous silica isoporous membrane (SIM) was prepared and integrated into a facile microfluidic chip for the desalting of protein samples based on dialysis principle. Thanks to the uniform pore size (∼2.3 nm in diameter), ultrasmall thickness (90 nm) and high pore density (4.0 × 1012 pores cm-2, corresponding to a porosity of 16.7%) of SIM, the device achieved ∼99% desalting efficiency for the sample with 154 mM NaCl (isotonic saline) at a flow rate of 1 µL min-1, while protein loss was only 5%. High-quality electrospray ionization (ESI)-MS spectra of cytochrome c dissolved in isotonic saline was obtained after the desalting treatment. In addition, the SIM-based microfluidic device was successfully online-coupled with microchip ESI-MS for real-time desalting and characterization of proteins.

Study of Hybrid PVA/MA/TEOS Pervaporation Membrane and Evaluation of Energy Requirement for Desalination by Pervaporation.

Desalination by pervaporation is a membrane process that is yet to be realized for commercial application. To investigate the feasibility and viability of scaling up, a process engineering model was developed to evaluate the energy requirement based on the experimental study of a hybrid polyvinyl alcohol/maleic acid/tetraethyl orthosilicate (PVA/MA/TEOS) Pervaporation Membrane. The energy consumption includes the external heating and cooling required for the feed and permeate streams, as well as the electrical power associated with pumps for re-circulating feed and maintaining vacuum. The thermal energy requirement is significant (e.g., up to 2609 MJ/m³ of thermal energy) and is required to maintain the feed stream at 65 °C in recirculation mode. The electrical energy requirement is very small (<0.2 kWh/m³ of required at 65 °C feed temperature at steady state) with the vacuum pump contributing to the majority of the electrical energy. The energy required for the pervaporation process was also compared to other desalination processes such as Reverse Osmosis (RO), Multi-stage Flash (MSF), and Multiple Effect Distillation (MED). The electrical energy requirement for pervaporation is the lowest among these desalination technologies. However, the thermal energy needed for pervaporation is significant. Pervaporation may be attractive when the process is integrated with waste heat and heat recovery option and used in niche applications such as RO brine concentration or salt recovery.

Biological fuel cells produce bioelectricity with in-situ brackish water purification.

Biological fuel cells, namely microbial desalination cells (MDCs) are a promising alternative to traditional desalination technologies, as microorganisms can convert the energy stored in wastewater directly into electricity and utilize it in situ to drive desalination, producing a high-quality reuse water. However, there are several challenges to be overcome in order to scale up from laboratory research. This study was conducted in order to better understand the performance of MDCs inoculated with marine sediments during the treatment of brackish water (5.0 g L-1 of NaCl) under three different configurations and cycles of desalination, envisaging the future treatment of saline wastewaters with conductivities lower than 10 mS cm-1. Results have shown that by increasing the desalination cycle three times, the efficiency of salt removal was improved by 3.4, 2.4 and 2.3 times for 1-MDC, 3-MDC, and 5-MDC, respectively. The same trend was observed for electrochemical data. Findings encourage further development of the MDC for sustainable brackish water and wastewater purification and future on-site utilization.

Frequency analysis and resonant operation for efficient capacitive deionization.

Capacitive deionization (CDI) performance metrics can vary widely with operating methods. Conventional CDI operating methods such as constant current and constant voltage show advantages in either energy or salt removal performance, but not both. We here develop a theory around and experimentally demonstrate a new operation for CDI that uses sinusoidal forcing voltage (or sinusoidal current). We use a dynamic system modeling approach, and quantify the frequency response (amplitude and phase) of CDI effluent concentration. Using a wide range of operating conditions, we demonstrate that CDI can be modeled as a linear time invariant system. We validate this model with experiments, and show that a sinusoid voltage operation can simultaneously achieve high salt removal and strong energy performance, thus very likely making it superior to other conventional operating methods. Based on the underlying coupled phenomena of electrical charge (and ionic) transfer with bulk advection in CDI, we derive and validate experimentally the concept of using sinusoidal voltage forcing functions to achieve resonance-type operation for CDI. Despite the complexities of the system, we find a simple relation for the resonant time scale: the resonant time period (frequency) is proportional (inversely proportional) to the geometric mean of the flow residence time and the electrical (RC) charging time. Operation at resonance implies the optimal balance between absolute amount of salt removed (in moles) and dilution (depending on the feed volume processed), thus resulting in the maximum average concentration reduction for the desalinated water. We further develop our model to generalize the resonant time-scale operation, and provide responses for square and triangular voltage waveforms as two examples. To this end, we develop a general tool that uses Fourier analysis to construct CDI effluent dynamics for arbitrary input waveforms. Using this tool, we show that most of the salt removal (∼95%) for square and triangular voltage forcing waveforms is achieved by the fundamental Fourier (sinusoidal) mode. The frequency of higher Fourier modes precludes high flow efficiency for these modes, so these modes consume additional energy for minimal additional salt removed. This deficiency of higher frequency modes further highlights the advantage of DC-offset sinusoidal forcing for CDI operation.

Hydrodynamic classification of submerged Thermal-Saline Inclined Single-Port discharges.

The discharge of warm effluent from thermal power plants and saline effluent from desalination sites in aquatic environments can, if the sufficient dilution is not attained, subsequently lead to severe environmental damage in the water column or surrounding waterbed. This paper attempted to experimentally assess an inclined single-port discharge system for thermal-saline effluent in a still, homogeneous water environment. The experiments were conducted for different combinations of salinity and warmth of the effluent and at three discharge angles of 30°, 45° and 60°. The results of this study developed a classification chart for Thermal-Saline Inclined Single-Port jets. In fact, the charts are applicable to thermal-saline jets with a new layer added to the charts proposed in previous studies for positive and negative jets. This research has also provided the criteria for thermal-saline buoyant jets to design, including the discharge angle and the proper combinations of effluent salinity and warmth.

Self similarities in desalination dynamics and performance using capacitive deionization.

Charge transfer and mass transport are two underlying mechanisms which are coupled in desalination dynamics using capacitive deionization (CDI). We developed simple reduced-order models based on a mixed reactor volume principle which capture the coupled dynamics of CDI operation using closed-form semi-analytical and analytical solutions. We use the models to identify and explore self-similarities in the dynamics among flow rate, current, and voltage for CDI cell operation including both charging and discharging cycles. The similarity approach identifies the specific combination of cell (e.g. capacitance, resistance) and operational parameters (e.g. flow rate, current) which determine a unique effluent dynamic response. We here demonstrate self-similarity using a conventional flow between CDI (fbCDI) architecture, and we hypothesize that our similarity approach has potential application to a wide range of designs. We performed an experimental study of these dynamics and used well-controlled experiments of CDI cell operation to validate and explore limits of the model. For experiments, we used a CDI cell with five electrode pairs and a standard flow between (electrodes) architecture. Guided by the model, we performed a series of experiments that demonstrate natural response of the CDI system. We also identify cell parameters and operation conditions which lead to self-similar dynamics under a constant current forcing function and perform a series of experiments by varying flowrate, currents, and voltage thresholds to demonstrate self-similarity. Based on this study, we hypothesize that the average differential electric double layer (EDL) efficiency (a measure of ion adsorption rate to EDL charging rate) is mainly dependent on user-defined voltage thresholds, whereas flow efficiency (measure of how well desalinated water is recovered from inside the cell) depends on cell volumes flowed during charging, which is determined by flowrate, current and voltage thresholds. Results of experiments strongly support this hypothesis. Results show that cycle efficiency and salt removal for a given flowrate and current are maximum when average EDL and flow efficiencies are approximately equal. We further explored a range of CC operations with varying flowrates, currents, and voltage thresholds using our similarity variables to highlight trade-offs among salt removal, energy, and throughput performance.

Influence of biomass acclimation on the performance of a partial nitritation-anammox reactor treating industrial saline effluents.

The performance of the partial nitritation/anammox processes was evaluated for the treatment of fish canning effluents. A sequencing batch reactor (SBR) was fed with industrial wastewater, with variable salt and total ammonium nitrogen (TAN) concentrations in the range of 1.75-18.00 g-NaCl L-1 and 112 - 267 mg-TAN L-1. The SBR operation was divided into two experiments: (A) progressive increase of salt concentrations from 1.75 to 18.33 g-NaCl L-1; (B) direct application of high salt concentration (18 g-NaCl L-1). The progressive increase of NaCl concentration provoked the inhibition of the anammox biomass by up to 94% when 18 g-NaCl L-1 were added. The stable operation of the processes was achieved after 154 days when the nitrogen removal rate was 0.021 ± 0.007 g N/L·d (corresponding to 30% of removal efficiency). To avoid the development of NOB activity at low salt concentrations and to stabilize the performance of the processes dissolved oxygen was supplied by intermittent aeration. A greater removal rate of 0.029 ± 0.017 g-N L-1 d-1 was obtained with direct exposure of the inoculum to 18 g-NaCl L-1 in less than 40 days. Also, higher specific activities than those from the inoculum were achieved for salt concentrations of 15 and 20 g-NaCl L-1 after 39 days of operation. This first study of the performance of the partial nitritation/anammox processes, to treat saline wastewaters, indicates that the acclimation period can be avoided to shorten the start-up period for industrial application purposes. Nevertheless, further experiments are needed in order to improve the efficiency of the processes.

The influences of separators on capacitive deionization systems in the cycle of adsorption and desorption.

This research focused on the influence of different separator compartments on the performance of capacitive deionization (CDI) cells in terms of brackish water treatment. For comparison, different separators including filter paper(FP), carbon nanotube (CNT), and stainless steel fiber (SSF) on deionization and desorption rate of salt were examined. The best performance was obtained when the CNT separator was packed, followed by SSF and FP. Reducing the cell voltage from 1.2 to 0.4 V decreased the salt removal and electrode regeneration rate of SSF-CDI. Electrochemical impedance spectrometry (EIS) analysis revealed that the resistance and specific capacitance of separator materials are essential to the desalination and desorption performance of CDI. The electric double layers (EDLs) accelerated the ion transfer in the flow chamber due to storing excess ions, therefore increasing the desalination and electrode regeneration rate.

Concentration-Gradient Multichannel Flow-Stream Membrane Capacitive Deionization Cell for High Desalination Capacity of Carbon Electrodes.

We present a novel multichannel membrane flow-stream capacitive deionization (MC-MCDI) concept with two flow streams to control the environment around the electrodes and a middle channel for water desalination. The introduction of side channels to our new cell design allows operation in a highly saline environment, while the feed water stream in the middle channel (conventional CDI channel) is separated from the electrodes with anion- and cation-exchange membranes. At a high salinity gradient between side (1000 mm) and middle (5 mm) channels, MC-MCDI exhibited an unprecedented salt-adsorption capacity (SAC) of 56 mg g-1 in the middle channel with charge efficiency close to unity and low energy consumption. This excellent performance corresponds to a fourfold increase in desalination performance compared to the state-of-the-art in a conventional CDI cell. The enhancement originates from the enhanced specific capacitance in high-molar saline media in agreement with the Gouy-Chapman-Stern theory and from a double-ion desorption/adsorption process of MC-MCDI through voltage operation from -1.2 to +1.2 V.

Forward Osmosis in Wastewater Treatment Processes.

In recent years, membrane technology has been widely used in wastewater treatment and water purification. Membrane technology is simple to operate and produces very high quality water for human consumption and industrial purposes. One of the promising technologies for water and wastewater treatment is the application of forward osmosis. Essentially, forward osmosis is a process in which water is driven through a semipermeable membrane from a feed solution to a draw solution due to the osmotic pressure gradient across the membrane. The immediate advantage over existing pressure driven membrane technologies is that the forward osmosis process per se eliminates the need for operation with high hydraulic pressure and forward osmosis has low fouling tendency. Hence, it provides an opportunity for saving energy and membrane replacement cost. However, there are many limitations that still need to be addressed. Here we briefly review some of the applications within water purification and new developments in forward osmosis membrane fabrication.

Greening Drylands with Seawater Easily and Naturally.

The sun and sea are inexhaustible sources of energy and water that could be used to transform drylands into more viable ecosystems. A sustainable and cost-effective approach is proposed for greening drylands and restoring wildlife and biodiversity in deserts using seawater desert-houses (or movable seawater ponds) that could offer important environmental advantages.

Bioinspired materials for water supply and management: water collection, water purification and separation of water from oil.

Access to a safe supply of water is a human right. However, with growing populations, global warming and contamination due to human activity, it is one that is increasingly under threat. It is hoped that nature can inspire the creation of materials to aid in the supply and management of water, from water collection and purification to water source clean-up and rehabilitation from oil contamination. Many species thrive in even the driest places, with some surviving on water harvested from fog. By studying these species, new materials can be developed to provide a source of fresh water from fog for communities across the globe. The vast majority of water on the Earth is in the oceans. However, current desalination processes are energy-intensive. Systems in our own bodies have evolved to transport water efficiently while blocking other molecules and ions. Inspiration can be taken from such to improve the efficiency of desalination and help purify water containing other contaminants. Finally, oil contamination of water from spills or the fracking technique can be a devastating environmental disaster. By studying how natural surfaces interact with liquids, new techniques can be developed to clean up oil spills and further protect our most precious resource.This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'.

Toward high permeability, selectivity and controllability of water desalination with FePc nanopores.

Nanoporous materials exhibit promising potential in water transportation applications, especially in ocean water desalination. It is highly desired to have great permeability, selectivity and controllability in the desalination performance of these nanopores. However, it is still a challenge to achieve all three features in one material or device. Here, we demonstrate efficient and controllable water desalination with a nanoporous 2D Fe phthalocyanine (FePc) membrane using molecular dynamics simulations. We find the FePc membrane not only conducts fast water flow, but it also suppresses ion permeation. The selectivity is attributed to a mechanism distinct from the traditional steric exclusion: cations are excluded due to electrostatic repulsion, whereas anions can be trapped in the nanopore and induce the reorganization of ions in the vicinity of the nanopore, which in turn creates a tendency for the trapped anions to move back into the saline reservoir. More interestingly, we find such mechanism is largely due to the sufficiently strong electrostatic interaction of the charged nanopore region with ions and is not restricted to the FePc nanopore. In addition, the number of protonated nitrogen atoms in FePc pores can be modulated by adjusting the pH value of the solution. The extent of the anion occupancy can thus be regulated, giving rise to control of the water flow. Taken together, great permeability, selectivity and controllability can be achieved with this nanosheet system. Moreover, our study suggests there is an alternative mechanism of water desalination which may be realized by intrinsically nanoporous materials such as FePc membranes.