Thorough Validation of Optimized Size Exclusion Chromatography-Total Organic Carbon Analysis for Natural Organic Matter in Fresh Waters.

Size exclusion chromatography with total organic carbon detection (HPSEC-TOC) is a widely employed technique for characterizing aquatic natural organic matter (NOM) into high, medium, and low molecular weight fractions. This study validates the suitability of HPSEC-TOC for a simplified yet efficient routine analysis of freshwater and its application within drinking water treatment plants. The investigation highlights key procedural considerations for optimal results and shows the importance of sample preservation by refrigeration with a maximum storage duration of two weeks. Prior to analysis, the removal of inorganic carbon is essential, which is achieved without altering the NOM composition through sample acidification to pH 6 and subsequent N2-purging. The chromatographic separation employs a preparative TSK HW-50S column to achieve a limit of detection of 19.0 µgC dm-3 with an injection volume of 1350 mm-3. The method demonstrates linearity up to 10,000 µgC dm-3. Precision, trueness and recovery assessments are conducted using certified reference materials, model compounds, and real water samples. The relative measurement uncertainty in routine analysis ranges from 3.22% to 5.17%, while the measurement uncertainty on the bias is 8.73%. Overall, the HPSEC-TOC represents a reliable tool for NOM fractions analysis in both treated and untreated ground and surface water.

Selective separation of nutrients and volatile fatty acids from food wastes using electrodialysis and membrane contactor for resource valorization.

Transport and selectivity parameters describe the quantity and purity of nutrients and volatile fatty acids (VFAs) separated from fermentation media. However, the complexity of fermentation media and low nutrient concentrations hinder the optimal conditions of such parameters. Exploring technologies to overcome such limitations is crucial for selectively separating VFAs from nutrients in fermented media. The objectives of this study were to investigate the: (1) flux, (2) recovery, (3) concentration factor, and (4) specific energy consumption of nutrients (NH4+, K+, NO3-, and PO43-) and VFAs (acetic, propionic, and butyric acid) via electrodialysis (ED), and (5) selectively separate the VFAs from the nutrients in the ED concentrate using a hydrophobic membrane contactor (HMC). Synthetic feed and real industrial fermented food wastes were used for ED and HMC experiments. The ED consumed 0.395 kWh/kg, recovering 64-95% of the nutrients and VFAs, corresponding to 4.1-9.4 and 0.6-22.1 g/L nutrients and VFAs, respectively. The HMC selectively separated over 94% of VFAs after ED, with <2% nutrients contamination in the final VFA stream. The results suggest that applying HMC after ED can concentrate and selectively separate VFAs from nutrients in fermented food wastes, which can be valorized for bio-based fertilizers and chemical platforms.

Fate of organic micropollutants during brackish water desalination for drinking water production in decentralized capacitive electrodialysis.

Capacitive electrodialysis (CED) is an emerging and promising desalination technology for decentralized drinking water production. Brackish water, often used as a drinking water source, may contain organic micropollutants (OMPs), thus raising environmental and health concerns. This study investigated the transport of OMPs in a fully-functional decentralized CED system for drinking water production under realistic operational conditions. Eighteen environmentally-relevant OMPs (20 µg L-1) with different physicochemical properties (charge, size, hydrophobicity) were selected and added to the feed water. The removal of OMPs was significantly lower than that of salts (∼94%), mainly due to their lower electrical mobility and higher steric hindrance. The removal of negatively-charged OMPs reached 50% and was generally higher than that of positively-charged OMPs (31%), whereas non-charged OMPs were barely transported. Marginal adsorption of OMPs was found under moderate water recovery (50%), in contrast to significant adsorption of charged OMPs under high water recovery (80%). The five-month operation demonstrated that the CED system could reliably produce water with low salt ions and TOC concentrations, meeting the respective WHO requirements. The specific energy consumption of the CED stack under 80% water recovery was 0.54 kWh m-3, which is competitive to state-of-the-art RO, ED, and emerging MCDI in brackish water desalination. Under this condition, the total OPEX was 2.43 € m-3, of which the cost of membrane replacement contributed significantly. Although the CED system proved to be a robust, highly adaptive, and fully automated technology for decentralized drinking water production, it was not highly efficient in removing OMPs, especially non-charged OMPs.

Non-steady diffusion and adsorption of organic micropollutants in ion-exchange membranes: effect of the membrane thickness.

There is no efficient wastewater treatment solution for removing organic micropollutants (OMPs), which, therefore, are continuously introduced to the Earth's surface waters. This creates a severe risk to aquatic ecosystems and human health. In emerging water treatment processes based on ion-exchange membranes (IEM), transport of OMPs through membranes remains unknown. We performed a comprehensive investigation of the OMP transport through a single IEM under non-steady-state conditions. For the first time, positron annihilation lifetime spectroscopy was used to study differences in the free volume element radius between anion- and cation-exchange membranes, and between their thicknesses. The dynamic diffusion-adsorption model was used to calculate the adsorption and diffusion coefficients of OMPs. Remarkably, diffusion coefficients increased with the membrane thickness, where its surface resistance was more evident in thinner membranes. Presented results will contribute to the improved design of next-generation IEMs with higher selectivity toward multiple types of organic compounds.

Transport of organic solutes in ion-exchange membranes: Mechanisms and influence of solvent ionic composition.

Ion-exchange membrane (IEM)-based processes are used in the industry or in the drinking water production to achieve selective separation. The transport mechanisms of organic solutes/micropollutants (i.e., paracetamol, clofibric acid, and atenolol) at a single-membrane level in diffusion cells were similar to that of salts (i.e., diffusion, convection, and electromigration). The presence of an equal concentration of salts at both sides of the membrane slightly decreased the transport of organics due to lower diffusion coefficients of organics in salts and the increase of hindrance and/or decrease of partitioning in the membrane phase. In the presence of a salt gradient, diffusion was the main transport mechanism for non-charged organics, while the counter-transport of salts promoted the transport of charged organics through electromigration (electroneutrality). Conversely, the co-transport of salts hindered the transport of charged organics, where diffusion was the main transport mechanism of the latter. Although convection played a role in the transport of non-charged organics, its influence on the charged solutes was minimal due to the dominant electromigration. Positron annihilation lifetime spectroscopy showed a bimodal size distribution of free-volume elements of IEMs, with both classes of free-volume elements contributing to salt transport, while larger organics can only transport through the larger class.

Impact of salt accumulation in the bioreactor on the performance of nanofiltration membrane bioreactor (NF-MBR)+Reverse osmosis (RO) process for water reclamation.

The impacts of salt accumulation, through adjusting the solid retention time (SRT), in the bioreactor on the bioprocess as well as membrane performance of a high retention nanofiltration membrane bioreactor (NF-MBR) and subsequent reverse osmosis (RO) process for water reclamation are addressed in this study. The build-up of salts (i.e., Ca, Mg, PO4) is a function of SRT, hydraulic retention time (HRT) and membrane rejection. Despite the accumulation of salts, both NF-MBRs at SRT of 30 and 60 days, achieved (i) similar biodegradation efficiency; (ii) excellent organic removal (> 97%); and (iii) excellent ammonia removal (> 98%). Extending the SRT could improve the microbial bio-flocculation capability, but did not influence the microbial activity, viability, and community structure. However, more severe membrane fouling was observed in the NF-MBR with elevated salt levels, which was attributed to the greater formation of calcium phosphate scale and Ca-polysaccharides complex (i.e., irreversible fouling layer) as well as the cake-enhanced-osmotic-pressure (CEOP) effect. Although both NF-MBRs produced comparable quality of permeate, a higher RO membrane fouling rate was observed when the permeate of NF-MBR with SRT at 60 days was fed to the RO system, implying organic compositions in NF-MBR permeate may influence RO performance.

Impact of isolated dissolved organic fractions from seawater on biofouling in reverse osmosis (RO) desalination process.

The biofouling potential of three isolated dissolved organic fractions from seawater according to their molecular weights (MWs), namely, fractions of biopolymers (F.BP, MW > 1000 Da), humic substances and building blocks (F.HS&BB, MW 350-1000 Da), and low molecular weight compounds (F.LMW, MW < 350 Da) were characterized by assimilable organic carbon (AOC) content. The AOC/DOC ratio was in the order of F.LMW (∼35%) > F.BP (∼19%) > F.HS&BB (∼8%); AOC/DOC of seawater was ∼20%; organic compositions of seawater were BP ∼6%, HS&BB ∼52% and LMW ∼42%; LMW accounted for >70% of AOC in seawater. Their impact on SWRO biofouling in term of flux decline rate was in the order of F. LMW (∼30%) > F.BP (∼20%) > F.HS&BB (<10%). Despite being the major organic compound in seawater, HS&BB showed marginal effect on biofouling. The role of indigenous BP was less critical owing to its relatively low concentration. LMW, which was the major AOC contributor, played a significant role in biofouling by promoting microbial growth that contributed to the build-up of soluble microbial products and exopolymeric substances (i.e., in particular BP). Therefore, seawater pretreatment shall focus on the removal of AOC (i.e., LMW) rather than the removal of biopolymer.

Development and application of relevance and reliability criteria for water treatment removal efficiencies of chemicals of emerging concern.

With the growth in production and use of chemicals and the fact that many end up in the aquatic environment, there is an increasing need for advanced water treatment technologies that can remove chemicals of emerging concern (CECs) from water. The current lack of a homogenous approach for testing advanced water treatment technologies hampers the interpretation and evaluation of CEC removal efficiency data, and hinders informed decision making by stakeholders with regard to which treatment technology could satisfy their specific needs. Here a data evaluation framework is proposed to improve the use of current knowledge in the field of advanced water treatment technologies for drinking water and wastewater, consisting of a set of 9 relevance criteria and 51 reliability criteria. The two criteria sets underpin a thorough, unbiased and standardised method to select studies to evaluate and compare CEC removal efficiency of advanced water treatment technologies in a scientifically sound way. The relevance criteria set was applied to 244 papers on removal efficiency, of which only 20% fulfilled the criteria. The reliability criteria were applied to the remaining papers. In general these criteria were fulfilled with regards to information on the target compound, the water matrix and the treatment process conditions. However, there was a lack of information on data interpretation and statistics. In conclusion, a minority of the evaluated papers are suited for comparison across techniques, compounds and water matrixes. There is a clear need for more uniform reporting of water treatment studies for CEC removal. In the future this will benefit the selection of appropriate technologies.

Fouling behavior of isolated dissolved organic fractions from seawater in reverse osmosis (RO) desalination process.

Organic fouling is still elusive in seawater reverse osmosis (SWRO) desalination process. Classifying organics in seawater will provide an in-depth understanding of the important fraction on RO fouling. In this study, dissolved organic matter (DOM) in seawater was fractionated and concentrated by membrane technique into three major fractions (i.e., biopolymer fraction, humic substance with building block fraction, and low molecular weight fraction) by their molecular weight (MW) according to the definitions in liquid chromatography with organic carbon detection (LC-OCD) method. Overall recovery of >80% was attained. The isolated organic fractions were compared with common model foulants such as sodium alginate (SA), bovine serum albumin (BSA), and humic acid (HA), in terms of chemical analyses using fluorescence-excitation emission matrix (FEEM) and LC-OCD, as well as their fouling potentials. SWRO fouling experiments were carried out and fouling mechanism was investigated by atomic force microscopy (AFM) method and extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory. Results showed that initial fouling (i.e., foulant-membrane interaction) was the main driver in SWRO organic fouling with biopolymer fraction as the major contributor followed by low molecular weight fraction. In addition, divalent ions was found to enhance the RO fouling by increasing the adhesion and cohesion forces between foulant-membrane and foulant-foulant.

Fate and removal of trace pollutants from an anion exchange spent brine during the recovery process of natural organic matter and salts.

The results of this sampling campaign on pilot scale processes aim to evaluate the occurrence and behavior of trace organic micro-pollutants and metal elements during anion exchange treatment of surface water and the subsequent treatment of generated spent brine with two types of electrodialysis membrane pairs. This knowledge is relevant to assess the quality and reusability of secondary products created during brine treatment; specifically the excess of sodium chloride to be recycled onsite and the natural organic matter, mostly consisting of humic substances, which find multiple applications in the agricultural industry. This study highlights that (1) the attachment mechanism of organic micro-pollutants to anion exchange resin occurs through electrostatic interaction and the subsequent transfer through ion exchange membranes is restricted by size exclusion; and (2) the complexation of trace metals compounds with the natural organic matter partly explains their removal by anion exchange. Complexes remain stable during treatment of the brine with electrodialysis.

Removal of polar organic micropollutants by pilot-scale reverse osmosis drinking water treatment.

The robustness of reverse osmosis (RO) against polar organic micropollutants (MPs) was investigated in pilot-scale drinking water treatment. Experiments were carried in hypoxic conditions to treat a raw anaerobic riverbank filtrate spiked with a mixture of thirty model compounds. The chemicals were selected from scientific literature data based on their relevance for the quality of freshwater systems, RO permeate and drinking water. MPs passage and the influence of permeate flux were evaluated with a typical low-pressure RO membrane and quantified by liquid chromatography coupled to high-resolution mass spectrometry. A strong inverse correlation between size and passage of neutral hydrophilic compounds was observed. This correlation was weaker for moderately hydrophobic MPs. Anionic MPs displayed nearly no passage due to electrostatic repulsion with the negatively charged membrane surface, whereas breakthrough of small cationic MPs could be observed. The passage figures observed for the investigated set of MPs ranged from less than 1%-25%. Statistical analysis was performed to evaluate the relationship between physicochemical properties and passage. The effects of permeate flux were more pronounced for small neutral MPs, which displayed a higher passage after a pressure drop.

Online monitoring of transparent exopolymer particles (TEP) by a novel membrane-based spectrophotometric method.

The presence of transparent exopolymer particles (TEP) in water bodies has been related to several adverse impacts in various water treatment processes. In recent years, there have been an increasing number of publications relating to TEP. Unfortunately, this increased interest in TEP measurement has not been accompanied by significant improvement in the analysis method or TEP monitoring. Currently, the most common method to analyze and quantify TEP only allows offline, and often offsite measurement, causing delays and slow response times. This paper introduces an improved method for TEP monitoring using a membrane-based spectrophotometric technique to quantify TEP in various water bodies. The proposed TEP monitor involves a crossflow filtration unit, reagent injection and a spectrophotometer system. The TEP retained on the membrane surface is stained by Alcian blue and the amount deposited is quantified directly using an optic fibre reflectance probe coupled with a spectrophotometer. The novel method shows a linear relationship with various concentrations of Xanthan gum (a model representing TEP). When tested with various water samples, the proposed method was found to correlate well with the conventional method. Several advantages of this novel method are shorter analysis time, increased accuracy, and the potential to be further developed into an online system.

Potable Water Reuse through Advanced Membrane Technology.

Recycling water from municipal wastewater offers a reliable and sustainable solution to cities and regions facing shortage of water supply. Places including California and Singapore have developed advanced water reuse programs as an integral part of their water management strategy. Membrane technology, particularly reverse osmosis, has been playing a key role in producing high quality recycled water. This feature paper highlights the current status and future perspectives of advanced membrane processes to meet potable water reuse. Recent advances in membrane materials and process configurations are presented and opportunities and challenges are identified in the context of water reuse.

The feasibility of nanofiltration membrane bioreactor (NF-MBR)+reverse osmosis (RO) process for water reclamation: Comparison with ultrafiltration membrane bioreactor (UF-MBR)+RO process.

This study examines the feasibility of a novel nanofiltration membrane bioreactor (NF-MBR) followed by reverse osmosis (RO) process for water reclamation at 90% recovery and using an ultrafiltration MBR (UF-MBR)+RO as baseline for comparison. Both MBRs adopted the same external hollow fiber membrane configurations and operating conditions. The collected permeates of the MBRs were subsequently fed to the respective RO systems. The results showed that the NF-MBR (operated at a constant flux of 10 L/m2h) achieved superior MBR permeate quality due to enhanced biodegradation and high rejection capacity of the NF membrane, leading to lower RO fouling rates (∼3.3 times) as compared to the UF-MBR. Further analysis indicated that the cake layer fouling that caused the cake-enhanced osmotic pressure (CEOP) effect contributed predominantly to the transmembrane pressure (TMP) increase in the NF-MBR, while irreversible pore fouling was the major reason for UF membrane fouling. Furthermore, it was found that the biopolymers (i.e., organics with MW > 10 kDa) were the main components present in the foulants of the NF/UF membranes and RO membranes. The analysis indicated that the NF-MBR + RO system at recovery of 90% has comparable energy consumption as the UF-MBR + RO system at recovery of 75%. Our findings proved the feasibility of the NF-MBR + RO for water reclamation at a high recovery rate.

Hydrogel-coated feed spacers in two-phase flow cleaning in spiral wound membrane elements: a novel platform for eco-friendly biofouling mitigation.

Biofouling is still a major challenge in the application of nanofiltration and reverse osmosis membranes. Here we present a platform approach for environmentally friendly biofouling control using a combination of a hydrogel-coated feed spacer and two-phase flow cleaning. Neutral (polyHEMA-co-PEG10MA), cationic (polyDMAEMA) and anionic (polySPMA) hydrogels have been successfully grafted onto polypropylene (PP) feed spacers via plasma-mediated UV-polymerization. These coatings maintained their chemical stability after 7 days incubation in neutral (pH 7), acidic (pH 5) and basic (pH 9) environments. Anti-biofouling properties of these coatings were evaluated by Escherichia coli attachment assay and nanofiltration experiments at a TMP of 600 kPag using tap water with additional nutrients as feed and by using optical coherence tomography. Especially the anionic polySPMA-coated PP feed spacer shows reduced attachment of E. coli and biofouling in the spacer-filled narrow channels resulting in delayed biofilm growth. Employing this highly hydrophilic coating during removal of biofouling by two-phase flow cleaning also showed enhanced cleaning efficiency, feed channel pressure drop and flux recoveries. The strong hydrophilic nature and the presence of negative charge on polySPMA are most probably responsible for the improved antifouling behavior. A combination of polySPMA-coated PP feed spacers and two-phase flow cleaning therefore is promising and an environmentally friendly approach to control biofouling in NF/RO systems employing spiral-wound membrane modules.

EDTA: a synthetic draw solute for forward osmosis.

The draw solution is the driving force of the forward osmosis (FO) process; however, the solute loss of the draw solute to the feed side is a general, financial limitation for most applications. The anthropogenic amino acid ethylenediaminetetraacetic acid (EDTA) was investigated as a draw solution for FO. At concentrations of approximately 1.0 osmol/kg, EDTA demonstrated comparable water fluxes (Jv = 5.29 L/m(2) h) to the commonly used salt, NaCl (Jv = 4.86 L/m(2) h), and both produced better water fluxes than glucose (Jv = 3.46 L/m(2) h). EDTA showed the lowest solute loss with Js (reverse solute loss or solute leakage) = 0.54 g/m(2) h. The molecular weight, degree of ionisation and charge of EDTA played a major role in this efficiency and EDTA was therefore well rejected by the membrane, showing a low Js/Jv ratio of 0.10 g/L. Owing to the low solute loss of EDTA and its resistance to biodegradation, this compound has the potential to be used as a draw solute for FO during long periods without requiring much replenishment.

Assessing the effect of surface modification of polyamide RO membrane by l-DOPA on the short range physiochemical interactions with biopolymer fouling on the membrane.

Theoretical predictions of interaction energies for membrane-biopolymer foulant pairs were used to compare the fouling tendencies of a virgin commercial polyamide reverse osmosis (RO) membrane with a amino acid 3-(3,4-dihydroxyphenyl)-l-alanine (l-DOPA) coated RO membrane. Lifshitz-van der Waals (LW) and Lewis acid-base (AB) surface tension components of the membranes were determined based on contact angle results using the van Oss approach. From these values, the LW and AB components of the free energy of adhesion between membrane and foulants were calculated. Electrostatic (EL) double layer interaction energies between the membrane and foulants were also estimated using the measured surface charge data of the membranes and fouling agents. Bovine serum albumin (BSA) and alginic acid sodium salt (alginate) were used as model biopolymers causing membrane fouling. Based on the calculated adhesion free energies, acid-base interactions were found to have the strongest impact on the adhesion of both BSA and alginate to the either membranes surfaces. It was found that l-DOPA modification has significantly lowered acid-base interaction affinity toward the adhesion of both foulants studied. On the basis of calculated free energies of adhesion, lower fouling tendency of the l-DOPA modified membrane was expected. The accelerated fouling tests indicated a lower flux decline rate for the modified membrane and confirmed the results obtained from theory.

Facile fouling resistant surface modification of microfiltration cellulose acetate membranes by using amino acid L-DOPA.

A major obstacle in the widespread application of microfiltration membranes in the wet separation processes such as wastewater treatment is the decline of permeates flux as a result of fouling. This study reports on the surface modification of cellulose acetate (CA) microfiltration membrane with amino acid L-3,4-dihydroxy-phenylalanine (L-DOPA) to improve fouling resistance of the membrane. The membrane surface was characterised using Fourier transform infrared spectroscopy (FTIR), water contact angle and zeta potential measurement. Porosity measurement showed a slight decrease in membrane porosity due to coating. Static adsorption experiments revealed an improved resistance of the modified membranes towards the adhesion of bovine serum albumin (BSA) as the model foulant. Dead end membrane filtration tests exhibited that the fouling resistance of the modified membranes was improved. However, the effect of the modification depended on the foulant solution concentration. It is concluded that L-DOPA modification is a convenient and non-destructive approach to enable low-BSA adhesion surface modification of CA microfiltration membranes. Nevertheless, the extent of fouling resistance improvement depends on the foulant concentration.

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.