Pharmaceutical rejection by membranes for wastewater reclamation and reuse.

Various membranes, which have different materials and nominal molecular weight cut-offs (MWCO), were compared in terms of rejection of ibuprofen and removal of effluent organic matter (EfOM) from membrane bioreactor (MBR), because pharmaceutical compounds contain a potential risk and EfOM is the precursor of carcinogenic disinfection by-products when reusing for drinking water source. To provide equivalent comparison with respect to hydrodynamic condition, mass transfer parameter, J0/k ratio, was used. A tight-UF membrane with a molecular weight cut off of 8,000 daltons exhibited 25 approximately 95% removal efficiencies of ibuprofen with a molecular weight of 206 with and without presence of EfOM(MBR). EfOM(MBR) caused the reduction of ibuprofen removal efficiency for UF membrane. Rejection of EfOM(MBR) by UF and NF membranes ranged 29 approximately 47% and 69 approximately 86%, respectively. UF membrane could successfully remove ibuprofen at lower J0/k ratio range (< or = 1) in organic free water but could not efficiently reject ibuprofen with a relatively hydrophilic EfOM(MBR) (SUVA < or = 3).     

Differentiation of wastewater effluent organic matter (EfOM) from natural organic matter (NOM) using multiple analytical techniques.

Using three analytical techniques of size exclusion chromatography (SEC), fluorescence excitation-emission matrix (EEM), and dissolved organic nitrogen (DON) measurement, differentiating characteristics of effluent organic matter (EfOM) from natural organic matter (NOM) have been investigated. SEC reveals a wide range of molecular weight (MW) for EfOM and high amount of high MW polysaccharides, and low MW organic acids compared to NOM. Clear protein-like peaks using fluorescence EEM were a major feature of EfOM distinguishing it from NOM. Fluorescence index (FI), an indicator to distinguish autochthonous origin from allochthonous origin, differentiated EfOM from NOM by exhibiting higher values, indicating a microbial origin. In EfOM samples, DON present in higher amounts than NOM.     

Membrane-flocculation-adsorption hybrid system in wastewater treatment: micro and nano size organic matter removal .

Cross flow microfiltration with in-line flocculation reduces the fouling of membranes thus leading to high quality product water. A detailed experimental study conducted with an artificial suspension (particle size distribution similar to that of surface water) revealed that the filtration rate can be increased by several times by adopting in-line flocculation. In-line flocculation-microfiltration is therefore an attractive technique to reduce internal clogging while improving the permeate flux significantly. A detailed ultrafiltration (UF) study was conducted with biologically treated sewage effluent with pretreatment by flocculation and powdered activated carbon adsorption. The TOC removal by the NTR 7410 UF membrane alone was 43.6%. The TOC removal increased significantly by the use of pretreatment: 69.3% by flocculation and 91% by flocculation followed by adsorption. The organic colloidal portion (between 3,500 dalton and 0.45 microm) in the biologically treated effluent was removed up to more than 65% by the pretreatment of flocculation. The molecular weight of the biologically treated effluent ranged from 250 to about 3,573 dalton with the highest fraction in the range of 250-845 dalton. By the incorporation of pretreatment, the majority of both large and small molecular weight organic matter was removed. This hybrid system led to practically no filtration flux decline in membrane filtration.     

Influence of organic and colloidal fouling on the removal of sulphamethoxazole by nanofiltration membranes.

This study investigated the effects of organic and colloidal fouling on the removal of a representative micropollutant sulphamethoxazole by two commercially available NF membranes. Alginate, bovine serum albumin and colloidal silica were selected as model foulants to simulate hydrophilic and hydrophobic organic fractions, and colloidal matter that are often found in treated effluent and surface water. Membrane fouling was related to the membrane and foulant characteristics and subsequently the separation behaviour of the micropollutant sulphamethoxazole under different solution pH. On the basis of these results, it was confirmed that membrane fouling is strongly dependent on both the foulant and membrane characteristics. The complex relationship among retention mechanisms, fouling mechanisms and the effects of fouling on retention was systematically delineated. Of the three model foulants selected for this study, colloidal fouling resulted in the most significant reduction in retention of sulphamethoxazole as well as inorganic salts, while flux decline as a result of colloidal fouling was quite moderate. Reduction in retention caused by fouling was attributed to a phenomenon known as cake-enhance concentration polarisation, which was a predominant mechanism of colloidal fouling. In addition, the reported results suggested that the effect of fouling on retention is also membrane pore size dependent.     

Assessing chemical cleaning of nanofiltration membranes in a drinking water production plant: a combination of chemical composition analysis and fluorescence microscopy.

The efficiency of cleaning procedures to remove the fouling deposit from the surface of NF membranes operating in the drinking water plant of Méry sur Oise (Val d'Oise, France) was assessed by a combination of chemical analysis and fluorescence microscopy. The ATR-FTIR spectra of the fouled membranes revealed the presence of biological matter at the membrane surface, mainly composed of polysaccharides, nucleic acids and proteins. IR bands corresponding to the membrane material were detected for stage 1 but not for stage 3. Confocal laser scanning microscopy (CLSM) observations confirmed the microbial origin of the fouling deposit. After chemical cleaning, the analysis of the inorganic foulants revealed a significant decrease of the inorganic content. Moreover, ATR-FTIR spectra of the fouled membranes were modified, mainly in a broad complex region corresponding to polysaccharides and nucleic acids. The amide bands were also altered for stage 1, and some peaks corresponding to the clean membrane appeared for stage 3 after cleaning. CLSM observations revealed a general decrease of the lectin staining for the two stages with some variations between lectins. A decrease of the DAPI staining indicative of the removal of some microbial cells was also observed for stage 1. In conclusion, cleaning of the NF fouled membranes decreased significantly the inorganic foulants but only partially removed the organic fouling deposit characteristic of a microbial biofilm.     

膜生物反应器长期运行条件下膜的清洗方法及机理研究

对实际工程中运行2年以上的MBR的膜使用能谱分析、傅立叶红外光谱和接触角测定等方法对膜表面的污染物特性进行了分析,对膜清洗过程中不同清洗剂的作用效果进行了探讨,并进一步对膜污染过程进行了推测.结果表明,酸性清洗剂对膜的清洗效果较好,膜表面无机污染基本被去除,但不能完全有效去除膜表面有机酸、蛋白质、多糖和多糖类物质等有机污染物;NaOH和NaClO对污染后的膜的清洗效果不佳,原因可能是由于MBR进水为混凝沉淀池出水,长期运行条件下膜污染以无机污染为主,有机污染可能起到了螯合的作用,使无机污染物和有机污染物络合,增加了碱和氧化剂去除有机污染的难度.     

Assessing the removal potential of soil-aquifer treatment systems for bulk organic matter.

The fate of effluent organic matter (EfOM) during groundwater recharge was investigated by studying the removal behavior of four bulk organic carbon fractions isolated from a secondary effluent: Hydrophilic organic matter (HPI), hydrophobic acids (HPO-A), colloidal organic matter (OM), and soluble microbial products (SMPs). Short-term removal of the bulk organic fractions during soil infiltration was simulated in biologically active soil columns. Results revealed that the four organic fractions showed a significantly different behavior with respect to biological removal. HPI and colloidal OM were prone to biological removal during initial soil infiltration (0-30 cm) and supported soil microbial biomass growth in the infiltrative surface. Additionally, colloidal OM was partly removed by physical adsorption or filtration. HPO-A and SMPs reacted recalcitrant towards biological degradation as indicated by low soil biomass activity responses. Adsorbability assessment of the biologically refractory portions of the fractions onto powered activated carbon (PAC) indicated that physical removal is not likely to play a significantly role in further diminishing recalcitrant HPO-A, HPI and SMPs during longer travel times in the subsurface.     

Fate of effluent organic matter (EfOM) and natural organic matter (NOM) through riverbank filtration.

Understanding the fate of effluent organic matter (EfOM) and natural organic matter (NOM) through riverbank filtration is essential to assess the impact of wastewater effluent on the post treatment requirements of riverbank filtrates. Furthermore, their fate during drinking water treatment can significantly determine the process design. The objective of this study was to characterise bulk organic matter which consists of EfOM and NOM during riverbank filtration using a suite of innovative analytical tools. Wastewater effluent-derived surface water and surface water were used as source waters in experiments with soil columns. Results showed the preferential removal of non-humic substances (i.e. biopolymers) from wastewater effluent-derived surface water. The bulk organic matter characteristics of wastewater effluent-derived surface water and surface water were similar after 5 m soil passage in laboratory column experiment. Humic-like organic matter in surface water and wastewater effluent-derived surface water persisted through the soil passage. More than 50% of total dissolved organic carbon (DOC) removal with significant reduction of dissolved oxygen (DO) was observed in the top 50 cm of the soil columns for both surface water and wastewater effluent-derived surface water. This was due to biodegradation by soil biomass which was determined by adenosine triphosphate (ATP) concentrations and heterotrophic plate counts. High concentrations of ATP in the first few centimeters of infiltration surface reflect the highest microbial activity which correlates with the extent of DOC reduction. Good correlation of DOC removal with DO and biomass development was observed in the soil columns.     

Evaluation of a long-term operation of a submerged nanofiltration membrane bioreactor (NF MBR) for advanced wastewater treatment.

Nanofiltration (NF) is considered as one of the most promising separation technologies to obtain a very good-quality permeate in water and wastewater treatment. A submerged NF membrane bioreactor (NF MBR) using polyamide membranes was tested for a long-term operation and the performance of the NF MBR was compared with that of a microfiltration MBR (MF MBR). Total organic carbon (TOC) concentration in the permeate of the NF MBR ranged from 0.5 to 2.0 mg/L, whereas that of the MF MBR showed an average of 5 mg/L. This could be explained by the tightness of the NF membrane. Although the concentration of organic matter in the supernatant of the NF MBR was higher than that in the permeate due to high rejection by the NF membrane, the NF MBR showed excellent treatment efficiency and satisfactory operational stability for a long-term operation.     

Use of nanofiltration for potable water from an aquifer recharged with wastewater.

This paper presents the comparison of nine nanofiltration membranes to treat water coming from an aquifer recharged with wastewater and used as municipal supply in the Tula Valley, Mexico. The comparison was made based on (a) the amount of water produced; (c) the capability to produce a <1 mg TOC/L effluent without entirely eliminating salts, (b) the removal of specific organic and microbiological pollutants, and (c) the reduction of toxicity and mutagenicity from water. From the tested membranes, only four produce an effluent with <1 TOC mg/L, and three totally retained dibutyl phthalate, diethyl phthalate and hydroxytoluene butylate. Influent mutagenicity (Ames test) was negative but these was a certain degree of toxicity when Tetrahymena pyriformis was used as indicator. Toxicity was partially reduced by some of the NF membranes. The best membrane had a flux of 95 L m(-2)h(-1) and removal efficiencies of 98% for TOC, 92% for AUV(254), and 92% for TDS. The permeate had a final hardness of 76 mg/L and an alkalinity of 124 mg/L. Additionally, this membrane removed totally specific organic compounds, total and fecal coliforms and almost all the somatic coliphages.     

Simultaneous visualisation of biofouling, organic and inorganic particle fouling on separation membranes.

Fouling is a major problem in membrane processes of water treatment. It can be caused by the deposition of inorganic and organic particulate material, and of microbial cells which may subsequently form biofilms. In practice, usually more than one foulant participates in the formation of membrane deposits. Knowledge of the composition of fouling layers is important for the development of appropriate countermeasures. For this purpose, an experimental system was established for the generation and microscopic visualisation of mixed deposits, using fluorescently labelled model foulants: (i) drinking-water bacteria stained with nucleic acid-specific dyes (biofouling), (ii) synthetic clay mineral laponite stained with rhodamine 6G (inorganic particle fouling), and (iii) fluorescently labelled polystyrene microspheres (organic particle fouling). Polycarbonate and polyethersulfone membranes were challenged with these foulants by dead-end filtration. On the basis of different fluorescent labels, the single foulants in these mixed deposits could be visualised separately by confocal laser scanning microscopy which, in combination with image analysis, allowed the generation of three-dimensional views of the complete deposits. This method offers the possibility for the estimation of quantitative surface coverage by foulants and for the determination of the efficacy of cleaning measures with respect to the removal of different foulants.     

Post-treatment of biologically treated wastewater of agrochemical industry by sulfated chitosan composite nanofiltration membrane

The objective of this study is to treat the biologically treated wastewater using sulfated chitosan/ polyacrylonitrile (PAN) composite nanofiltration (NF) membrane to improve agrochemical industry wastewater quality for reuse. Although biological treatment is quite efficient, the wastewater does not meet the reuse criteria. Hence, further treatment to improve the water quality is investigated. Sulfated chitosan composite NF membranes, having a PAN ultrafiltration membrane as the substrate, are prepared by coating and cross-linking methods. The effects of membrane preparation conditions on the rejection and permeation performance of the membranes are studied. The new membranes are characterized by NMR and scanning electron micrograph. Wastewater from agrochemical industry contains high concentrations of organic matter, color, heavy metals and other toxic substances. The operating variables studied are applied pressure (3-15 atm) and feed flowrate (4-16 L/min). It is found that the observed rejection (R(o)) increases with increase in feed pressure at constant feed flowrate. The rejection of cations follows the sequence: R(o)(Zn2+) > R(o)(Ni2+) > R(o)(CU2+) > R(o)(Cd2+) for wastewater. It is observed that the order of solute rejection sequence is inversely proportional to the diffusion coefficients.     

Rejection of trace organic compounds by high-pressure membranes.

High-pressure membranes, encompassing reverse osmosis (RO), nanofiltration (NF), and low-pressure RO, may provide an effective treatment barrier for trace organic compounds including disinfection by-products (DBPs), pesticides, solvents, endocrine disrupting compounds (EDCs) and pharmaceutically active compounds (PhACs). The objective is to develop a mechanistic understanding of the rejection of trace organic compounds by high-pressure membranes, based on an integrated framework of compound properties, membrane properties, and operational conditions. Eight trace organic compounds, four DBPs and four chlorinated (halogenated) solvents, are being emphasized during an initial study, based on considerations of compound properties, occurrence, and health effects (regulations). Four polyamide FilmTec membranes; three reverse osmosis/RO (BW-400, LE-440, XLE-440) and one nanofiltration/NF (NF-90); are being characterized according to pure water permeability (PWP), molecular weight cutoff (MWCO), hydrophobicity (contact angle), and surface charge (zeta potential). It is noteworthy that rejections of compounds of intermediate hydrophobicity by the candidate membranes were observed to be less than salt rejections reported for these membranes, suggesting that transport of these solutes through these membranes is facilitated by solute-membrane interactions. We are continuing with diffusion cell measurements to describe solute-membrane interactions by estimation of diffusion coefficients through membranes pores, either hindered or facilitated.     

Investigation of membrane fouling in ultrafiltration using model organic compounds.

Natural organic matter (NOM) is known to be the worst foulant in the membrane processes, but the complexities of NOM make it difficult to determine its effects on membrane fouling. Therefore, simple organic compounds (surrogates for NOM) were used in this research to investigate the fouling mechanisms in ultrafiltration. Previous research on NOM components in membrane processes indicated that polysaccharides formed an important part of the fouling cake. Three polysaccharides (dextran, alginic acid, and polygalacturonic acid) and a smaller carbohydrate (tannic acid) were evaluated for their removal in softening (the treatment process in the City of Austin). Two polysaccharides (dextran and alginic acid) were selected and further investigated for their effects on membrane fouling. The two raw organic waters (4 mg/L C) showed quite different patterns of flux decline indicating different fouling mechanisms. Softening pretreatment was effective to reduce flux decline of both waters. The SEM images of the fouled membrane clearly showed the shapes of deposited foulants. The high resolution results of the XPS spectra showed substantially different spectra of carbon, C(1s), in the membrane fouled by two raw organic waters. The XPS was beneficial in determining the relative composition of each fouling material on the membrane surface.     

Importance of the order in enhancing EfOM removal by combination of BAC and MIEX(?)

Biological activated carbon (BAC) is operationally a simple treatment which can be employed to remove effluent organic matter (EfOM) from secondary wastewater effluent (SWWE). Unfortunately, BAC removes only a limited amount of dissolved organic carbon (DOC). Thus, maximizing DOC removal from SWWE using BAC is a major concern in wastewater reuse. This study has investigated a hybrid system of BAC and Magnetic Ion Exchange Resin (MIEX(?)) for the enhanced removal of DOC. Performance of both BAC prior to MIEX(?) (BAC/MIEX(?)) and reverse (MIEX(?)/BAC) combination was evaluated in terms of DOC removal. The BAC/MIEX(?) showed much better DOC removal. This is because microbial activity in the BAC bed converted MIEX(?) non-amenable DOC to MIEX(?) amenable DOC. As a result, BAC/MIEX(?) combination synergised DOC removal. In addition, BAC was also found to be highly effective in reducing MIEX(?) dose for a given DOC removal from SWWE.     

Effect of recirculation on organic matter removal in a hybrid constructed wetland system

This research project aimed to determine the technologically feasible and applicable wastewater treatment systems which will be constructed to solve environmental problems caused by small communities in Turkey. Pilot-scale treatment of a small community's wastewater was performed over a period of more than 2 years in order to show applicability of these systems. The present study involves removal of organic matter and suspended solids in serially operated horizontal (HFCW) and vertical (VFCW) sub-surface flow constructed wetlands. The pilot-scale wetland was constructed downstream of anaerobic reactors at the campus of TUBITAK-MRC. Anaerobically pretreated wastewater was introduced into this hybrid two-stage sub-surface flow wetland system (TSCW). Wastewater was first introduced into the horizontal sub-surface flow system and then the vertical flow system before being discharged. Recirculation of the effluent was tested in the system. When the recirculation ratio was 100%, average removal efficiencies for TSCW were 91 +/- 4% for COD, 83 +/- 10% for BOD and 96 +/- 3% for suspended solids with average effluent concentrations of 9 +/- 5 mg/L COD, 6 +/- 3 mg/L BOD and 1 mg/L for suspended solids. Comparing non-recirculation and recirculation periods, the lowest effluent concentrations were obtained with a 100% recirculation ratio. The effluent concentrations met the Turkish regulations for discharge limits of COD, BOD and TSS in each case. The study showed that a hybrid constructed wetland system with recirculation is a very effective method of obtaining very low effluent organic matter and suspended solids concentrations downstream of anaerobic pretreatment of domestic wastewaters in small communities.     

Organic and detergent degradation in combined O3/UF for domestic laundry wastewater reclamation.

This paper focuses on the evaluation of organic and detergent degradation in a combined Ozone/UF system for domestic laundry wastewater reclamation. Formation of by-product was investigated by GC/MS for the reclaimed water. Ozone was injected into the raw wastewater in a 10 L contact tank and the wastewater was circulated through the membrane module for inner pressurized cross-flow filtration. The concentrate was returned back to the contact tank. The membrane used in this experiment was hollow fiber polysulfone UF membrane with MWCO 10,000. It has an effective filtration area of 0.06 m2. The experiment was carried out with intermittent ozone injection, 5 min injection and 10 min idling. Ozone was dosed at the concentration of 1.5 mg/L. The flux of the UF could be maintained at 0.24 m/d under filtration pressure 40-45 kPa and water temperature, 20-22 degrees C. The organic removal efficiency by the system was 90% in terms of COD. Ozone was considerably effective to degrade organics in the wastewater. Molecular weight of organics in the raw waste was mostly greater than 10,000 (72% of 950 mgCOD/L). However 86% of effluent COD (94-100 mg/L) was composed of organics smaller than MWCO 500 by ozone injection. No harmful by-products by ozone contact were detected from the analysis of treated water using GC/MS. It was identified that residual organics in the treated water were 1,1'-Oxybisbenzene, Octadecanoic acid, Squalene and Benzenmethanol, etc., which were additives contained originally in the detergent. Consequently the reclaimed water quality could be estimated safe enough to recycle for the rinsing cycle in a washing machine.     

Influence of the size of membrane foulants on the filterability of WWTP-effluent.

The application of membrane filtration for the polishing of wastewater treatment plant (wwtp) effluent is more and more widely used. However, fouling problems are still not well understood. In order to investigate the role of particles in dead-end ultrafiltration of wwtp-effluent, Roorda studied the influence of pre-filtrated wwtp-effluent on the filterability. In addition this research investigates the relation between the filterability of the different fractions in the wwtp-effluent and the amount of organic foulants in these fractions. The results show a relation between the filterability and supra-dissolved particles in the fractions < 0.45 and < 0.2 microm. The amount of COD, colour, proteins and polysaccharides in these fractions are found of minor importance. A significant increase in filterability is found between the fractions < 0.2 and < 0.1 microm as well as a significant decrease in amount of polysaccharides. It is suggested that an essential feature in understanding membrane fouling during ultrafiltration of wwtp-effluent is to investigate the influence of supra-dissolved particles on the filterability as well as the influence of the amount of organic foulants (total organic carbon, proteins, polysaccharides, colour and humic substances) on the reversibility.     

Membrane filtration for tertiary treatment of biologically treated effluents from the pulp and paper industry.

Discharge waters from activated sludge processes in the pulp and paper industry and from a municipal wastewater treatment plant were filtered with various nanofiltration (NF) and low pressure reverse osmosis (RO) membranes. The purpose was to study flux, retention, and permeate quality after membrane filtration by using a high shear (CR-250/2) filter. The suitability of the achieved permeates for reuse at the industrial site is also discussed. The NF permeate was practically free from colour and organic compounds but contained significant amount of inorganic compounds e.g. chloride ions, especially when a high amount of sulphate containing discharge waters were filtered, in which case a low pressure RO membrane was needed to successfully remove monovalent anions. Organic compounds were almost completely retained by NF and RO membranes and organic carbon in the permeate was less than 10 mg/dm3 on average. The achieved permeate can easily be reused in paper production. Nanofiltration has a significantly higher flux and also a lower fouling tendency than reverse osmosis but it passes through monovalent ions when there is a high sulphate concentration in the water. Therefore, RO might be needed in such cases to produce excellent process water.     

Combined chemical biological treatment of bleached eucalypt kraft pulp mill effluent.

Effectiveness of ozonation before and after biological treatment for removal of recalcitrant organic matter in bleached kraft pulp effluents was compared. Two industrial ECF bleached eucalypt kraft pulp effluents (E1 and E2) were pretreated with 100 mg O3/L. Raw and pretreated effluents were treated biologically in bench-scale sequencing batch reactors, under constant conditions. Following biological treatment, effluents were post-treated with 100 and 200 mg O3/L. Effluent pretreatment increased effluent biodegradability by 10% in E1 and 24% in E2. Combined O3-biological treated led to small but significant increases in COD, BOD and lignin removal over biological treatment alone, but pretreatment had no significant effect on effluent colour and carbohydrate removal. Ozone pretreatment did not affect biological activity during treatment of effluent E1 but resulted in a 38% lower specific oxygen uptake rate in effluent E2. At an equivalent dose of 100 mg/L, pre-ozonation produced better quality effluent than post-ozonation, especially with regard to COD and colour. Likewise, when an equivalent dose of 200 mg/L was applied, splitting the dose equally between pre- and post-treatments was more efficient than applying the entire dose in the post-treatment. The potential for combined chemical-biological treatment to improve effluent quality has been confirmed in this study.