Electrosorptive removal of organic water constituents by positively charged electrically conductive UF membranes.

Negatively charged electrically conductive ultrafiltration (UF) membranes have been intensively investigated for fouling mitigation and rejection enhancement in recent years. This study reports the novel approach of applying positive charge (+2.5 V cell potential) to a conductive membrane to induce electrosorption of negatively charged substances onto the membrane. Subsequently, desorption of negatively charged substances is achieved by changing the potential periodically (e.g., after 30 min) to negative charge (-2.5 V cell potential). For this purpose, sputter deposition of ultra-thin gold layers (40 nm) is used to generate electrically conductive gold-polymer-gold flat sheet membranes by coating the active and the support layer of two commercial polymer UF membranes (polyethersulfone UP150, polyamide M5). When M5 membrane was charged positively during filtration (+2.5 V), Suwannee River NOM, Hohloh lake NOM, humic acid and Brilliant Blue ionic dye showed removal rates of 70 %, 75% and 93% and 99%, respectively. Whereas, when no potential was applied (0 V) removal rates were only 1 - 5 %. When a positive potential was applied to the active membrane layer and a negative potential was applied to the support layer (cell potential 2.5 V), a significant increase of flux with 25 L/(m² h) was observed due to the induction of electro-osmosis. Electrosorption was only observed for M5 membrane (ζ: +13 mV, pH 7) and not with UP150 membrane (ζ: -29 mV, pH 7). Due to a low current density of 1.1 A/m² at a flux of 100 L/(m² h), the additional energy consumption of electrosorption and desorption process was low with 0.03 kWh per m³ of permeate. This study delivered the proof of concept for the novel process of electrosorptive UF with energy consumption between microfiltration and ultrafiltration but NOM removal rates of nanofiltration membranes.

Identification and quantification of major organic foulants in treated domestic wastewater affecting filterability in dead-end ultrafiltration.

Ultrafiltration (UF) membranes can be used after conventional wastewater treatment to produce particle free and hygienically safe water for reuse. However, membrane fouling affects the performance of UF to a large extent. Stirred cell tests with UF membrane show high flux decline filtering treated domestic wastewater. Investigation on the impact of size fractioned substances indicates that dissolved substances are major foulants affecting water filterability. Dissolved organic substances in feed and permeate samples of the stirred cell tests are analyzed by liquid chromatography with online organic carbon detection (LC-OCD). The resulting chromatograms displayed a significant difference of feed and permeate samples in the range of large molecules identified as biopolymer peak. The substances detected in this peak (mostly macro polysaccharide-like and protein-like molecules) are almost completely retained by UF membranes. Quantified investigation shows that biopolymer concentration influences filterability of corresponding water sample proportionally. The apparent magnitude of delivered biopolymer to membrane has a striking correlation with fouling resistance. The relationship was verified to be reproducible using different water samples. Mechanism analysis demonstrates that based on the delivered biopolymer load to membrane pore blocking or cake/gel fouling is the main fouling mechanism in the present experiment conditions.

Complexity of ultrafiltration membrane fouling caused by macromolecular dissolved organic compounds in secondary effluents.

Recent investigations indicate the relevance of extracellular polymeric substances (EPS) in terms of fouling of low-pressure membranes in advanced wastewater treatment. In this study, the high impact of the macromolecular fraction of effluent organic matter on fouling was confirmed in cross-flow ultrafiltration experiments using secondary effluent with and without autochthonous biopolymers. A method for the extraction of a natural mixture of EPS derived from the bacterium Sinorhizobium sp. is presented. Ultrafiltration of solutions of this bacterial EPS extract revealed a correlation between the concentration of EPS and the loss of permeate flux. However, in ultrafiltration tests using extracted bacterial EPS in a model solution as well as in secondary effluent without autochthonous biopolymers, the extent of membrane fouling was not identical with the fouling provoked by secondary effluent organic matter, although the biopolymer concentrations were comparable. The differences in the fouling behaviour of the extracted bacterial EPS and effluent organic matter are considered to be due to different compositions of the biopolymer fraction in terms of proteins, polysaccharides, and other organic colloids, indicating a particular impact of proteins on ultrafiltration membrane fouling.

Impact of O3 or O3/H2O2 treatment via a membrane contacting system on the composition and characteristics of the natural organic matter of surface waters.

The present study aims to evaluate changes in the structure-composition of natural organic matter (NOM) that occur after the application of bubbleless ozonation or peroxone treatment of surface waters. The oxidation experiments (using 0.5-2 mg O3/mg DOC, or 2:1 O3:H2O2 molar ratio) were performed in a continuous mode, using a tubular ceramic membrane contactor. Fluorescence spectroscopy (emission-excitation matrix) and liquid chromatography-organic carbon detection (LC-OCD) were mainly used for the detailed DOC characterization. In brief, the application of single ozonation resulted to high reduction of humic-like peak fluorescence intensities (50-85%) and also to the formation of two new peaks in the region of protein-like components. The co-addition of H2O2 did not present the anticipated increase in the reduction of fluorescence intensity; however, it resulted to the further oxidation of protein-like fluorophores. LC-OCD measurements confirmed the decrease of average molecular weight of NOM during ozone treatment, due to the gradual degradation of biopolymers (14-23%) and humic substances (11-17%) towards building blocks and low molecular weight (LMW) neutrals. Advanced oxidation process (AOP) treatment by the mixture O3/H2O2 resulted in the simultaneous decrease of building blocks and LMW neutral concentrations. Conventional batch ozonation and AOP experiments were conducted using ozone-saturated solutions to investigate the effect of different contacting patterns. The results revealed that the different reaction pathways followed during bubbleless and conventional batch experiments may also influence the formation of NOM oxidation intermediates.

Impact of coagulation and adsorption on DOC fractions of secondary effluent and resulting fouling behaviour in ultrafiltration.

Membrane fouling by macromolecular dissolved organic compounds is still a fundamental drawback in low-pressure membrane filtration of secondary effluent. In this study, pre-treatment of secondary effluent by coagulation and/or adsorption was investigated in terms of removal of different dissolved organic carbon (DOC) fractions, especially macromolecular substances. DOC fractionation has been characterised by size exclusion chromatography. Adsorption tests using four commercially available activated carbons yielded a removal of small as well as larger organic compounds, revealing differences in the affinity towards macromolecules depending on the type of applied activated carbon. By contrast, coagulation removed predominantly larger molecules, i.e., biopolymers and humic substances. In terms of DOC reduction, the coagulant ferric chloride was superior to aluminium chloride. A combination of coagulation and adsorption resulted in the addition of individual removal efficiencies, suggesting that different fractions of organic compounds were involved in each of the processes. After removal of macromolecular organic compounds either by coagulation or by adsorption, a significant reduction of membrane fouling was observed in tests using two different types of ultrafiltration flat-sheet membranes in 20-h cross-flow filtration tests.

Correlations of relevant membrane foulants with UF membrane fouling in different waters.

Correlations between potential fouling-relevant substances and membrane fouling during ultrafiltration (UF) of different waters were investigated, including water samples from Lake Tegel, from a Berlin canal (Landwehrkanal) and from a wastewater treatment plant (WWTP) secondary effluent. The biopolymers quantified with liquid chromatography-organic carbon detection (LC-OCD) showed a remarkable correlation with UF membrane fouling for all the three water sources at different seasons. This finding suggests that the biopolymer content in water can be employed as a universal indicator for predicting membrane fouling potential in UF processes. The particulate matter in the two surface waters Lake Tegel and Berlin canal, as characterized by suspended solids and turbidity, also exhibited a distinct correlation with UF membrane fouling, although its correlation was slightly weaker than that of biopolymers. However, the humic substances, which are generally believed to be major membrane foulants, did not show any reliable correlation with the UF membrane fouling of the different waters. This work may provide useful information for the development of optimized fouling control strategies for sustainable UF operation.

Fate of antibiotics in activated sludge followed by ultrafiltration (CAS-UF) and in a membrane bioreactor (MBR).

The fates of several macrolide, sulphonamide, and trimethoprim antibiotics contained in the raw sewage of the Tel-Aviv wastewater treatment plant (WWTP) were investigated after the sewage was treated using either a full-scale conventional activated sludge (CAS) system coupled with a subsequent ultrafiltration (UF) step or a pilot membrane bioreactor (MBR) system. Antibiotics removal in the MBR system, once it achieved stable operation, was 15-42% higher than that of the CAS system. This advantage was reduced to a maximum of 20% when a UF was added to the CAS. It was hypothesized that the contribution of membrane separation (in both systems) to antibiotics removal was due either to sorption to biomass (rather than improvement in biodegradation) or to enmeshment in the membrane biofilm (since UF membrane pores are significantly larger than the contaminant molecules). Batch experiments with MBR biomass showed a markedly high potential for sorption of the tested antibiotics onto the biomass. Moreover, methanol extraction of MBR biomass released significant amounts of sorbed antibiotics. This finding implies that more attention must be devoted to the management of excess sludge.

Pilot-scale investigation on the removal of organic foulants in secondary effluent by slow sand filtration prior to ultrafiltration.

Natural biofiltration processes have been verified as effective pre-treatment choice improving the performance of low-pressure membranes (MF/UF) in wastewater reclamation. In the present work, pilot-scale slow sand filtration (SSF) was used to simulate bank filtration at high filtration rates (from 0.25m/h to 0.5m/h) to filter secondary effluent prior to UF. The results showed that SSF improved the performance of UF to a large extent. Related to previous work biopolymers are considered as major dissolved organic foulants in treated wastewater. The removal of these organic foulants in slow sand filters and factors affecting the performance of SSF were investigated. It was observed that the removal of biopolymers took place mainly at the upper sand layer and was related to biological degradation. Tests on the degradability of biopolymers verified that they are biodegradable. Sixteen months monitoring of biopolymer concentration in the secondary effluent indicated that it varied seasonally. In winter season the concentration was much higher than during the summer months. Higher temperature and lower biopolymer concentration led to more effective foulants removal and more sustainable operation of SSF. During the whole experimental period, the performance of SSF was always better at filtration rate of 0.25m/h than at 0.5m/h. Under the present experimental conditions, SSF exhibited stable and effective biopolymer removal at temperatures higher than 15 degrees C, at biopolymer concentrations lower than 0.5mg C/L and with sufficient oxygen available.

Biopolymer fouling in dead-end ultrafiltration of treated domestic wastewater.

Ultrafiltration (UF) is considered as a suitable treatment process after conventional wastewater treatment to produce reuse water. Nevertheless, fouling affects the performance of UF to a large extent. As biopolymers (mostly macro polysaccharide-like and protein-like molecules) have been identified as major foulants affecting the filterability of water in dead-end UF, the present study focuses on investigating the reversibility of biopolymer fouling occurring at different biopolymer mass loads to the membrane and under different compression conditions. UF-membrane stirred cell tests using five cycles show that filtering treated domestic wastewater leads to a significant permeability reduction due to the accumulation of biopolymers on the membrane surface and/or in the membrane pores. Although they can be removed by hydraulic backwashing, an increased mass load of biopolymers reduces the removal efficiency. This correlation was verified using a UF pilot plant filtering treated wastewater (secondary effluent or slow sand filtrate). The effect of biopolymer fouling layer deformation on its reversibility was studied using multi-cycle membrane filtration tests under different filtration pressures. The results showed that higher filtration pressures result in more compact biopolymer fouling which is more difficult to be hydraulically backwashed. This phenomenon was also confirmed by pilot-scale UF experiments.

Occurrence, source, and fate of dissolved organic matter (DOM) in a pilot-scale membrane bioreactor.

In this study, the fate of carbohydrates, proteins, and humic substances in feedwater, sludge supernatant, and permeate of a pilot-scale membrane bioreactor (MBR) was investigated. Over 10 months, carbohydrates were observed to have a lower bioelimination degree (45%) and higher rejection degree (79%) than those of proteins (81% and 44%, respectively), which led to a high carbohydrate/protein ratio of dissolved organic matter (DOM) in sludge supernatant. The batch tests showed that DOM derived from feedwater and bound extracellular polymeric substances (EPS) was eliminated by activated sludge via biosorption and biodegradation. The proteins in bound EPS and feedwater were also found to have much higher biosorption potential (27% and 31%, respectively) than humic substances (11% and 17%, respectively) and carbohydrates (16% and 14%, respectively), indicating that proteins had a high affinity with sludge flocs. The results also showed that carbohydrates and humic substances in bound EPS were more difficult to be eliminated by activated sludge. In addition, the batch tests confirmed that feedwater was mainly composed of readily biodegradable matter, and bound EPS was mainly composed of slowly biodegradable matter. Size exclusion chromatography with continuous organic carbon and UV(254) detection (LC-OCD) showed that large-size substances (i.e., carbohydrates and macromolecular proteins) in sludge supernatant might originate from bound EPS, which can be rejected by membranes. The LC-OCD analysis, together with the results obtained from batch tests, suggested bound EPS might be the most important source of DOM in the sludge suspension.