Electrochemically Induced Precipitation Enables Fresh Urine Stabilization and Facilitates Source Separation.

Source separation of urine can enable nutrient recycling, facilitate wastewater management, and conserve water. Without stabilization of the urine, urea is quickly hydrolyzed into ammonia and (bi)carbonate, causing nutrient loss, clogging of collection systems, ammonia volatilization, and odor nuisance. In this study, electrochemically induced precipitation and stabilization of fresh urine was successfully demonstrated. By recirculating the urine over the cathodic compartment of an electrochemical cell, the pH was increased due to the production of hydroxyl ions at the cathode. The pH increased to 11-12, decreasing calcium and magnesium concentrations by >80%, and minimizing scaling and clogging during downstream processing. At pH 11, urine could be stabilized for one week, while an increase to pH 12 allowed urine storage without urea hydrolysis for >18 months. By a smart selection of membranes [anion exchange membrane (AEM) with a cation exchange membrane (CEM) or a bipolar membrane (BPM)], no chemical input was required in the electrochemical cell and an acidic stream was produced that can be used to periodically rinse the electrochemical cell and toilet. On-site electrochemical treatment, close to the toilet, is a promising new concept to minimize clogging in collection systems by forcing controlled precipitation and to inhibit urea hydrolysis during storage until further treatment in more centralized nutrient recovery plants.

Properties governing the transport of trace organic contaminants through ion-exchange membranes.

Ion exchange membranes could provide a solution to the selective separation of organic and inorganic components in industrial wastewater. The phenomena governing the transport of organics through the IEM however, are not yet fully understood. Therefore, the transport of trace organic contaminants (TOrCs) as a model for a wide variety of organic compounds was studied under different conditions. It was found that in the absence of salt and external potential, the chemical equilibrium is the main driver for TOrC-transport, resulting in the transport of mainly charged TOrCs. When salt is present, the transport of TOrCs is hampered in favor of the NaCl transport, which shows a preferential interaction with the membranes due to its small size, high mobility and concentration. It is hypothesized that electrostatic interactions and electron donor/acceptor interactions are the main drivers for TOrC transport and that transport is mainly diffusion driven. This was confirmed in the experiments with different current densities, where the external potential seemed to have only a minor influence on the transport of TOrCs. It is only when the salt becomes nearly completely depleted that the TOrCs are transported as charge carriers. This shows that it is very difficult to get preferential transport of organic compounds due to the diffusive nature of their transport.

Surface characterisation of biofouled NF membranes: role of surface energy for improved rejection predictions.

Biomass attachment and growth on high pressure membranes alter the surface characteristics and rejection performance of nanofiltration membranes. Along with electrostatic interaction and size exclusion, hydrophobic interaction between solutes and membrane surface play the major role in the separation process. Therefore, in attempt to properly quantify the surface energy of clean and biofouled membranes, different contact angle techniques were applied in this research. The surface energies of membranes were determined on dry, wet and hydrated surfaces. Results indicate that drying of the membrane surface leads to a modification of the surface properties, which are therefore not representative of the membrane in its operational conditions. Immersing the membrane in water resulted in detachment of biomass material into the surrounding liquid, thus hampering a correct estimation of the contact angle. Contact angle measurements on hydrated surfaces, on the contrary, produced reproducible results, which are consistent with current knowledge. In addition, when the values obtained by hydrated method were applied in a predictive model earlier developed, a significant improvement in predictions resulted.

High-rate activated sludge systems combined with dissolved air flotation enable effective organics removal and recovery.

High-rate activated sludge (HRAS) systems typically generate diluted sludge which requires further thickening prior to anaerobic digestion (AD), besides the need to add considerable coagulant and flocculant for the solids separation. As an alternative to conventional gravitational settling, a dissolved air flotation (DAF) unit was coupled to a HRAS system or a high-rate contact stabilization (HiCS) system. The HRAS-DAF system allowed up to 78% removal of the influent solids, and the HiCS-DAF 67%. Both were within the range of values typically obtained for HRAS-settler systems, albeit at a lower chemical requirement. The separated sludge had a high concentration of up to 47 g COD L-1, suppressing the need of further thickening before AD. Methanation tests showed a biogas yield of up to 68% on a COD basis. The use of a DAF separation system can thus enable direct organics removal at high sludge concentration and with low chemical needs.

Refinery and concentration of nutrients from urine with electrodialysis enabled by upstream precipitation and nitrification.

Human urine is a valuable resource for nutrient recovery, given its high levels of nitrogen, phosphorus and potassium, but the compositional complexity of urine presents a challenge for an energy-efficient concentration and refinery of nutrients. In this study, a pilot installation combining precipitation, nitrification and electrodialysis (ED), designed for one person equivalent (1.2 Lurine d-1), was continuously operated for ∼7 months. First, NaOH addition yielded calcium and magnesium precipitation, preventing scaling in ED. Second, a moving bed biofilm reactor oxidized organics, preventing downstream biofouling, and yielded complete nitrification on diluted urine (20-40%, i.e. dilution factors 5 and 2.5) at an average loading rate of 215 mg N L-1 d-1. Batch tests demonstrated the halotolerance of the nitrifying community, with nitrification rates not affected up to an electrical conductivity of 40 mS cm-1 and gradually decreasing, yet ongoing, activity up to 96 mS cm-1 at 18% of the maximum rate. Next-generation 16S rRNA gene amplicon sequencing revealed that switching from a synthetic influent to real urine induced a profound shift in microbial community and that the AOB community was dominated by halophilic species closely related to Nitrosomonas aestuarii and Nitrosomonas marina. Third, nitrate, phosphate and potassium in the filtered (0.1 µm) bioreactor effluent were concentrated by factors 4.3, 2.6 and 4.6, respectively, with ED. Doubling the urine concentration from 20% to 40% further increased the ED recovery efficiency by ∼10%. Batch experiments at pH 6, 7 and 8 indicated a more efficient phosphate transport to the concentrate at pH 7. The newly proposed three-stage strategy opens up opportunities for energy- and chemical-efficient nutrient recovery from urine. Precipitation and nitrification enabled the long-term continuous operation of ED on fresh urine requiring minimal maintenance, which has, to the best of our knowledge, never been achieved before.

Efficiently Combining Water Reuse and Desalination through Forward Osmosis-Reverse Osmosis (FO-RO) Hybrids: A Critical Review.

Forward osmosis (FO) is a promising membrane technology to combine seawater desalination and water reuse. More specifically, in a FO-reverse osmosis (RO) hybrid process, high quality water recovered from the wastewater stream is used to dilute seawater before RO treatment. As such, lower desalination energy needs and/or water augmentation can be obtained while delivering safe water for direct potable reuse thanks to the double dense membrane barrier protection. Typically, FO-RO hybrid can be a credible alternative to new desalination facilities or to implementation of stand-alone water reuse schemes. However, apart from the societal (public perception of water reuse for potable application) and water management challenges (proximity of wastewater and desalination plants), FO-RO hybrid has to overcome technical limitation such as low FO permeation flux to become economically attractive. Recent developments (i.e., improved FO membranes, use of pressure assisted osmosis, PAO) demonstrated significant improvement in water flux. However, flux improvement is associated with drawbacks, such as increased fouling behaviour, lower rejection of trace organic compounds (TrOCs) in PAO operation, and limitation in FO membrane mechanical resistance, which need to be better considered. To support successful implementation of FO-RO hybrid in the industry, further work is required regarding up-scaling to apprehend full-scale challenges in term of mass transfer limitation, pressure drop, fouling and cleaning strategies on a module scale. In addition, refined economics assessment is expected to integrate fouling and other maintenance costs/savings of the FO/PAO-RO hybrid systems, as well as cost savings from any treatment step avoided in the water recycling.

Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption.

The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other.

Increasing RO efficiency by chemical-free ion-exchange and Donnan dialysis: Principles and practical implications.

Ion-exchange (IEX) and Donnan dialysis (DD) are techniques which can selectively remove cations, limiting scaling in reverse osmosis (RO). If the RO concentrate could be recycled for regeneration of these pre-treatment techniques, RO recovery could be largely increased without the need for chemical addition or additional technologies. In this study, two different RO feed streams (treated industrial waste water and simple tap water) were tested in the envisioned IEX-RO and DD-RO hybrids including RO concentrate recycling. The efficiency of multivalent cation removal depends mainly on the ratio of monovalent to multivalent cations in the feed stream, influencing the ion-exchange efficiency in both IEX and DD. Since the mono-to-multivalent ratio was very high in the waste water, the RO recovery could potentially be increased to 92%. For the tap water, these high RO recoveries could only be reached by adding additional NaCl, because of the low initial monovalent to multivalent ratio in the feed. In both cases, the IEX-RO hybrid proved to be most cost-efficient, due to the high current cost of the membranes used in DD. The membrane cost would have to decrease from ±300 €/m² to 10-30 €/m² - comparable to current reverse osmosis membranes - to achieve a comparable cost. In conclusion, the recycling of RO concentrate to regenerate ion exchange pre-treatment techniques for RO is an interesting option to increase RO recovery without addition of chemicals, but only at high monovalent/multivalent cation-ratios in the feed stream.

Tight ceramic UF membrane as RO pre-treatment: the role of electrostatic interactions on phosphate rejection.

Phosphate limitation has been reported as an effective approach to inhibit biofouling in reverse osmosis (RO) systems for water purification. The rejection of dissolved phosphate by negatively charged TiO2 tight ultrafiltration (UF) membranes (1 kDa and 3 kDa) was observed. These membranes can potentially be adopted as an effective process for RO pre-treatment in order to constrain biofouling by phosphate limitation. This paper focuses on electrostatic interactions during tight UF filtration. Despite the larger pore size, the 3 kDa ceramic membrane exhibited greater phosphate rejection than the 1 kDa membrane, because the 3 kDa membrane has a greater negative surface charge and thus greater electrostatic repulsion against phosphate. The increase of pH from 6 to 8.5 led to a substantial increase in phosphate rejection by both membranes due to increased electrostatic repulsion. At pH 8.5, the maximum phosphate rejections achieved by the 1 kDa and 3 kDa membrane were 75% and 86%, respectively. A Debye ratio (ratio of the Debye length to the pore radius) is introduced in order to evaluate double layer overlapping in tight UF membranes. Threshold Debye ratios were determined as 2 and 1 for the 1 kDa and 3 kDa membranes, respectively. A Debye ratio below the threshold Debye ratio leads to dramatically decreased phosphate rejection by tight UF membranes. The phosphate rejection by the tight UF, in combination with chemical phosphate removal by coagulation, might accomplish phosphate-limited conditions for biological growth and thus prevent biofouling in the RO systems.

Trace organic solutes in closed-loop forward osmosis applications: influence of membrane fouling and modeling of solute build-up.

In this study, trace organics transport in closed-loop forward osmosis (FO) systems was assessed. The FO systems considered, consisted of an FO unit and a nanofiltration (NF) or reverse osmosis (RO) unit, with the draw solution circulating between both units. The rejection of trace organics by FO, NF and RO was tested. It was found that the rejection rates of FO were generally comparable with NF and lower than RO rejection rates. To assess the influence of fouling in FO on trace organics rejection, FO membranes were fouled with sodium alginate, bovine serum albumin or by biofilm growth, after which trace organics rejection was tested. A negative influence of fouling on FO rejection was found which was limited in most cases, while it was significant for some compounds such as paracetamol and naproxen, indicating specific compound-foulant interactions. The transport mechanism of trace organics in FO was tested, in order to differentiate between diffusive and convective transport. The concentration of trace organics in the final product water and the build-up of trace organics in the draw solution were modeled assuming the draw solution was reconcentrated by NF/RO and taking into account different transport mechanisms for the FO membrane and different rejection rates by NF/RO. Modeling results showed that if the FO rejection rate is lower than the RO rejection rate (as is the case for most compounds tested), the added value of the FO-RO cycle compared to RO only at steady-state was small for diffusively and negative for convectively transported trace organics. Modeling also showed that trace organics accumulate in the draw solution.

Influence of biofouling on pharmaceuticals rejection in NF membrane filtration.

The effects of biomass attachment and growth on the surface characteristics and organic micropollutants rejection performance of nanofiltration membranes were investigated in a pilot installation. Biomass growth was induced by dosing of a readily biodegradable carbon source resulting in the formation of a biofouling in the investigated membrane elements. Surface properties and rejection behaviour of a biofouled and virgin membrane were investigated and compared in terms of surface charge, surface energy and hydrophobicity. The last two were accomplished by performing contact angle measurements on fully hydrated membrane surfaces, in order to mimic the operating conditions of a membrane in contact with water. Compared to a virgin membrane, deposition and growth of biofilm did slightly alter the surface charge, which became more negative, and resulted in a higher hydrophilicity of the membrane surface. In addition, the presence of the negatively charged biofilm induced accumulation of positively charged pharmaceuticals within the biomass layer, which probably also hindered back diffusion. This caused a reduction in rejection efficiency of positively charged solutes but did not alter rejection of neutral and negatively charged pharmaceuticals. Pharmaceuticals rejection was found to positively correlate with the specific free energy of interaction between virgin or biofouled membranes and pharmaceuticals dissolved in the water phase. The rejection values obtained with both virgin and biofouled membranes were compared and found in good agreement with the predictions calculated with a solute transport model earlier developed for high pressure filtration processes.

Influence of solute-membrane affinity on rejection of uncharged organic solutes by nanofiltration membranes.

A simple, analytical method for predicting transport of uncharged organic solutes through nanofiltration (NF) and reverse osmosis (RO) membranes is presented in this paper. The method requires characterization of key solute and membrane parameters-namely, solute size, membrane pore size, and solute-membrane affinity. All three parameters can be experimentally determined from relatively simple permeation tests and contact angle analyses. The parameters are fed into an analytical model of solute transport, which accounts for hindered convection and diffusion of solutes in the membrane pores, as well as the combined effects of steric exclusion and solute-membrane affinity on solute partitioning from the feed solution into the membrane pores. Overall model predictions for organic solute rejection agreed well with experimental data for three different solutes and two different polymeric NF membranes. Further, the model demonstrates the dramatic influence of solute-membrane affinity on organic rejection by NF and RO membranes. Solute transport predictions made assuming only steric exclusion significantly overestimated rejections for solutes with strong affinity for membrane polymers and similarly underestimated rejections for solutes that were strongly repelled by membrane polymers.