Review on the fate of organic micropollutants in wastewater treatment and water reuse with membranes

A brief review of the fate of micropollutants in membrane-based wastewater treatment due to sorption, stripping, biological degradation/transformation and membrane separation is discussed, to give an overview of these technologies due to the growing importance for water reuse purposes. Compared with conventional activated sludge treatment (CAS) micropollutant removal in membrane bioreactor (MBR) is slightly improved due to complete suspended solids removal and increased sludge age. For discharge to sensitive receiving waters advanced treatment, such as post-ozonation or activated carbon adsorption, is recommended. In water reuse plants nanofiltration (NF) and reverse osmosis (RO) efficiently reject micropollutants due to size exclusions as well as electrostatic and hydrophobic effects reaching potable quality. To remove micropollutants fully, additionally post-ozone or the addition of powdered activated carbon (PAC) have to be applied, which in parallel also reduce NDMA precursors. The concentrate has to be treated if disposed to sensitive receiving waters due to its high micropollutant concentration and ecotoxicity potential. The present review summarizes principles and capabilities for the most important membrane-based applications for wastewater treatment, i.e. porous membranes in MBRs (micro- or ultrafiltration) and dense membrane applications (NF and RO) for water reuse.     

Comparative study of MBR and activated sludge in the treatment of paper mill wastewater.

The study was based on a full scale activated sludge plant (AS) compared to a parallel operated pilot membrane bioreactor (MBR) with flat sheets membranes. Both systems received their influent from an anaerobic bioreactor treating paper mill wastewater. MBR produced an effluent of much better quality than AS in terms of suspended solids, containing 1 mg/L or less in 80% of the monitoring time, while the AS effluent contained 12 mg/L. This could save the necessity of further treatment by filtration in the case of MBR. Other effluent quality parameters, such as organic matter (COD and BOD), phosphorus and ammonia nitrogen, did not indicate substantial differences between AS and MBR. Calcium carbonate scaling and formation of a bacterial layer on the membrane caused severe flux reduction. The membrane blockage because of scaling and biofouling proved to be very serious, therefore, it required proper and more complicated maintenance than the AS system. This study leads to the conclusion that in the case of paper mill wastewater, after anaerobic biotreatment, if there is no need for excellent effluent quality in terms of suspended solids, the replacement of the AS by the MBR would not be strongly justified, mainly because of maintenance cost.     

The removal of residual organic matter from biologically treated swine wastewater using membrane bioreactor process with powdered activated carbon.

The objective of this study was to characterize the mechanisms of the COD removal in the membrane bioreactor (MBR) process with powdered activated carbon (PAC) addition and to determine its optimal operation, for the removal of residual organic matters (ROM) from biologically treated swine wastewater. The MBR process with PAC showed higher removal efficiency of chemical oxygen demand (COD(Mn)) than that without PAC. When the average COD(Mn) concentration of the influent was 217 mg/L, the average COD(Mn) concentration of the permeate from the MBR with PAC was about 41.5 mg/L, indicating an approximate removal efficiency of 81%. On the other hand, the average COD(Mn) concentration of the permeate from the MBR without PAC was 172 mg/L. The PAC dosage estimated to obtain the above removal efficiency was about 0.74 g per litre of influent. Among the total residual organics removed by PAC-added MBR, 46.5% was removed by PAC adsorption, 20.8% by biodegradation, 4.4% by membrane separation, and 9.3% by enhanced microorganism activity. From these results, the MBR process with PAC was considered as a very useful treatment process for the reduction of COD(Mn) in biologically treated swine wastewater.     

Characterization of sludge structure and activity in submerged membrane bioreactor.

Sludge characteristics of a submerged membrane bioreactor (MBR) and an activated sludge process (AS) were compared, during a first phase at the same operating conditions (low MLSS and conventional SRT) and in a second phase with a high sludge retention time (SRT) in the membrane bioreactor. During the first phase, a bimodal flocs size distribution was observed in the MBR with simultaneously a macro-flocs population (240 microm) bigger than the flocs of activated sludge due to the absence of recirculating pump, and also more microflocs (1 to 15 microm) and free suspended cells retained by the membrane. It is shown that the membrane leads to an accumulation of proteins and polysaccharides in the sludge supernatant which is probably responsible for the high fouling propensity of the sludge during the starting period of MBR. These compounds are partially degraded after 50 to 60 days of operation. In the first phase respirometric experiments didn't demonstrate a significant difference in the maximal removal rates of either MBR or AS biomass (with excess substrate), except in the dynamic period during which the membrane retention gave an advantage by increasing the biomass activity. On the other hand, the respirometry shows that the half saturation constant for nitrification was significantly higher in the MBR process, suggesting higher substrate transfer limitation. During the last phase, it is shown that an increase of SRT from 9 to 106 days leads to a diminution of average macro-flocs size in the MBR from about 240 to 70 microm. With the SRT increase, modification in the organic compounds is also observed (proteins, polysaccharides and COD) in the sludge supernatant. Increasing the SRT from 9 to 40 days seems to slightly reduce the level of organic compounds (probable biodegradation), but the concentrations increased when SRT changes from 40 days to 106 days (probable accumulation of non biodegradable compounds).     

Enhanced nutrient removal MBR system with chemical addition for low effluent TP

A pilot study was conducted to test an membrane bioreactor (MBR) process for combined biological and chemical P removal to achieve a very low effluent total phosphorus (TP) concentration of 0.025 mg P/L. With the data from the pilot test, a simulation study was performed to demonstrate that: (1) the pilot system behaviour (effluent quality, MLSS, etc.) can be modelled accurately with an activated sludge model combined with a chemical precipitation model; and (2) with the calibrated model, simulation scenarios can be performed to further understand the pilot MBR process, and provide information for optimizing design and operation when applied at full-scale. Results from the pilot test indicated that the system could achieve very low effluent TP concentration through biological P removal with a limited chemical addition, and chemical addition to remove P to very low level did not affect other biological processes, i.e., organic and nitrogen removal. Simulation studies indicate that the process behaviour can be modelled accurately with an activated sludge model combined with a chemical precipitation model, and the calibrated model can be used to provide information to optimize system design and operation, e.g., chemical addition control under dynamic loading conditions is important for maintaining biological P removal.     

Comparison of linear alkylbenzene sulfonates removal in conventional activated sludge systems and membrane bioreactors.

The potential of a membrane bioreactor (MBR) and a conventional activated sludge (CAS) system to remove polar micropollutants was evaluated using linear alkylbenzene sulfonates (LAS) as model components. Removal efficiencies over 97% were achieved in both reactor systems. The appearance of biological breakdown metabolites and the respirometric response of the sludges to LAS addition indicated that LAS removal was due to biodegradation, rather than sorption phenomena. The effect of operational variables, such as hydraulic retention time, LAS composition and hydrophobicity of the membrane used in the MBR, was negligible in the range tested. A stepwise increase in LAS influent concentration resulted in higher residual effluent concentrations but did not change the procentual removal efficiency. Because an increase in LAS and SPC effluent concentration occurred to a larger extent in the CAS than in the MBR under similar operating conditions, MBRs may turn out to be be more robust with respect to biological degradation of micropollutants than CAS.     

Advanced treatment by anaerobic process followed by aerobic membrane bioreactor for effluent reuse in paper mill industry.

The operation of an activated sludge process at a paper mill (AIPM) in Hedera, Israel, was often characterized by disturbances. As part of a research and development project, a study on new biological treatment was initiated. The study included the operation of three pilot units: a. anaerobic treatment by upflow anaerobic sludge blanket (UASB); b. aerobic treatment by two pilot units including activated sludge and membrane bioreactor (MBR), which have been operated in parallel for comparison reasons. The pilot plant working on anaerobic treatment performed COD reduction from 2,365 to 755 mg/L, expressed as average values. Based on the pilot study, a full scale anaerobic treatment system has been erected. During a period of 100 days, after achieving steady state, the MBR system provided steady operation performance, while the activated sludge produced effluent characterized by oscillatory qualities. The following results, based on average values, indicate much lower suspended solids concentrations in the MBR effluent, 2.5 mg/L, as compared to 25 mg/L in the activated sludge. The ability to develop and maintain a concentration of over 11,000 mg/L of mixed liquor volatile suspended solids in the MBR enabled an intensive bioprocess at relatively high cell residence time. This study demonstrates that the anaerobic process, followed by aerobic MBR can provide effluent of high quality which can be considered for economic reuse in the paper mill industry.     

Removal of inhibitory phenolic compounds by biological activated carbon coupled membrane bioreactor.

Phenolic compounds cause problems for conventional treatments due to their toxic and inhibitory properties. This work investigated the treatability of phenolic compounds by using two membrane-bioreactor systems, namely: activated sludge coupled with MBR (AS-MBR) and biological granular activated carbon coupled with MBR (BAC-MBR). Initially, the system was fed with phenol (500 mg/L) followed by adding 2,4-dichlorophenol (2,4-DCP). Phenol, 2,4-DCP, TOC and COD removal were higher than 98.99% when the organic load ranged between 1.80 and 5.76 kg/m3.d COD. In addition to MBR system development, removal mechanisms were also investigated. Relatively low values of phenol adsorption of GAC and biomass, and high maximum substrate removal rates obtained from a biokinetic experiment, proved that the removals were mainly due to biodegradation. Analysis of sludge indicated a significant difference in the sludge characteristics of the two reactors. The high EPS content in BAC-MBR led to higher viscosity and poor sludge settling properties. The relationship between sludge properties and EPS components revealed that settleability had no direct correlation with EPS, though it was better correlated to protein/carbohydrate ratios.     

Modelling of long-term simultaneous nitrification and denitrification (SNDN) performance of a pilot scale membrane bioreactor

Nutrient removal capability of the MBR process has attracted more attention than organics removal in the past few years. Apart from the conventional schemes for nitrogen removal in MBR process, simultaneous nitrification-denitrification (SNDN) requires the most attention for further research. In order to fully understand the fundemantals and mechanism of SNDN in MBRs, a pilot plant was set up. A mathematical model was adopted for investigation and calibration against the observed values. This paper reports a study focusing on evaluating major mechanisms that govern nitrogen removal from domestic wastewater in membrane bioreactors. Two items need to be emphasized in this evaluation: (i) an MBR is basically regarded as an activated sludge process-a suspended growth bioreactor with total biomass recycle and substantially higher biomass concentration; (ii) in this context an AS model, namely ASM1R modified for endogenous respiration, is used for dynamic modelling and calibration of experimental results. The impact of diffusion through biomass which obviously exerts a significant effect on system performance and denitrification is evaluated with success using the adopted model by means of switch functions that regulate nitrification-denitrification with respect to dissolved oxygen concentration in the bulk liquid.     

Biological nutrient removal in membrane bioreactors: denitrification and phosphorus removal kinetics.

The impact of including membranes for solid liquid separation on the kinetics of nitrogen and phosphorus removal was investigated. To achieve this, a membrane bioreactor (MBR) biological nutrient removal (BNR) activated sludge system was operated. From batch tests on mixed liquor drawn from the MBR BNR system, denitrification and phosphorus removal rates were delineated. Additionally the influence of the high total suspended solids concentrations present in the MBR BNR system and of the limitation of substrate concentrations on the kinetics was investigated. Moreover the ability of activated sludge in this kind of system to denitrify under anoxic conditions with simultaneous phosphate uptake was verified and quantified.The denitrification rates obtained for different mixed liquor (ML) concentrations indicate no effect of ML concentration on the specific denitrification rate. The denitrification took place at a single specific rate (K(2)) with respect to the ordinary heterotrophic organisms (OHOs, i.e. non-PAOs) active mass. Similarly, results have been obtained for the P removal process kinetics: no differences in specific rates were observed for different ML or substrate concentrations. From the P removal batch tests results it seems that the biological phosphorus removal population (PAO) consists of 2 different sets of organisms denitrifying PAO and aerobic PAO.     

Membrane bioreactor (MBR) sludge inoculation in a hybrid process scheme concept to assist overloaded conventional activated sludge (CAS) process operations

This study analyzes the effect of inoculating membrane bioreactor (MBR) sludge in a parallel-operated overloaded conventional activated sludge (CAS) system. Modelling studies that showed the beneficial effect of this inoculation were confirmed though full scale tests. Total nitrogen (TN) removal in the CAS increased and higher nitrate formation rates were achieved. During MBR sludge inoculation, the TN removal in the CAS was proven to be dependent on MBR sludge loading. Special attention was given to the effect of inoculation on sludge quality. The MBR flocs, grown without selection pressure, were clearly distinct from the more compact flocs in the CAS system and also contained more filamentous bacteria. After inoculation the MBR flocs did not evolve into good-settling compact flocs, resulting in a decreasing sludge quality. During high flow conditions the effluent CAS contained more suspended solids. Sludge volume index, however, did not increase. Laboratory tests were held to determine the threshold volume of MBR sludge to be seeded into the CAS reactor. Above 16-30%, supernatant turbidity and scum formation increased markedly.     

Occurrence of benzothiazoles in municipal wastewater and their fate in biological treatment.

A number of 2-substituted benzothiazoles that are known to be used as fungicides, corrosion inhibitors and vulcanization accelerators in industry have been analyzed in municipal wastewater and the effluents of activated sludge and membrane bioreactor (MBR) treatment over a three month period. All six analytes were regularly detected in the municipal wastewater by liquid chromatography-mass spectrometry and amount to a total concentration of 3.4 microg/L. Of these compounds benzothiazole-2-sulfonic acid (1,700 ng/L), benzothiazole (850 ng/L) and 2-hydroxybenzothiazole (500 ng/L) were most prominent. The source of the benzothiazole emission is yet unknown. Activated sludge treatment did not reduce total benzothiazole concentration significantly. Removals of the individual compounds ranged from 90% for 2-mercaptobenzothiazole and 70% for hydroxybenzothiazole to 40% for benzothiazole. The concentration of benzothiazole-2-sulfonic acid increased by 20%, whereas 2-methylthiobenzothiazole increased by 160% during activated sludge treatment, likely due to the methylation of mercaptobenzothiazole. Total benzothiazole removal in two parallely operated MBRs was significantly better (43%) than in the conventional activated sludge treatment. Namely benzothiazole and benzothiazole-2-sulfonic acid were more effectively removed. This first systematic study on the occurrence of benzothiazoles in municipal wastewater has shown that this is a relevant class of trace contaminants in municipal wastewater which is only incompletely removed in biological wastewater treatment. Emission from sewage treatment is dominated by the most polar benzothiazole-2-sulfonic acid. MBR treatment may reduce but cannot avoid this emission.     

MBR工艺处理城镇污水处理厂污泥水中试研究

将平板膜组件与传统脱氮除磷工艺相结合,构建了膜生物反应器强化生物脱氮除磷中试系统,并用于处理城镇污水处理厂的污泥系统废水。结果表明,出水CODCr、BOD5、NH3—N、TN和TP的平均浓度分别为70.8 mg/L、8.7 mg/L、15.1 mg/L、29.7 mg/L和0.38 mg/L,达到或接近了《城镇污水处理厂污染物排放标准》(GB 18918—2002)的一级标准。     

Long term operation of high concentration powdered activated carbon membrane bio-reactor for advanced water treatment.

A pilot scale experiment was conducted to evaluate the performance of a membrane bioreactor filled with high concentration powdered activated carbon. This hybrid system has great potential to substitute for existing GAC or O3/BAC processes in the drinking water treatment train. The system was installed at a water treatment plant located downstream of the Nakdong river basin, Korea. Effluent of rapid sand filter was used as influent of the system which consists of PAC bio-reactor, submerged MF membrane module and air supply facility. PAC concentration of 20 g/L was maintained at the beginning of the experiment and it was increased to 40 g/L. The PAC has not been changed during the operational periods. The membrane was a hollow fiber type with pore sizes of 0.1 and 0.4 microm. It was apparent that the high PAC concentration could prevent membrane fouling. 40 g/L PAC was more effective to reduce the filtration resistance than 20 g/L. At the flux of 0.36 m/d, TMP was maintained less than 40 kPa for about 3 months by intermittent suction type operation (12 min suction/3 min idling). Adsorption was the dominant role to remove DOC at the initial operational period. However the biological effect was gradually increased after around 3 months operation. Constant DOC removal could be maintained at about 40% without any trouble and then a tremendous reduction of DBPs (HAA5 and THM) higher than 85% was achieved. Full nitrification was observed at the controlled influent ammonia nitrogen concentration of 3 and 7 mg/L. pH was an important parameter to keep stable ammonia oxidation. From almost two years of operation, it is clear that the PAC membrane bioreactor is highly applicable for advanced water treatment under the recent situation of more stringent DBPs regulation in Korea.     

A comparison of BNR activated sludge systems with membrane and settling tank solid-liquid separation.

Installing membranes for solid-liquid separation into biological nutrient removal (BNR) activated sludge (AS) systems makes a profound difference not only to the design of the membrane bio-reactor (MBR) BNR system itself, but also to the design approach for the whole wastewater treatment plant (WWTP). In multi-zone BNR systems with membranes in the aerobic reactor and fixed volumes for the anaerobic, anoxic and aerobic zones (i.e. fixed volume fractions), the mass fractions can be controlled (within a range) with the inter-reactor recycle ratios. This zone mass fraction flexibility is a significant advantage of MBR BNR systems over BNR systems with secondary settling tanks (SSTs), because it allows changing the mass fractions to optimise biological N and P removal in conformity with influent wastewater characteristics and the effluent N and P concentrations required. For PWWF/ADWF ratios (fq) in the upper range (fq approximately 2.0), aerobic mass fractions in the lower range (f(maer) < 0.60) and high (usually raw) wastewater strengths, the indicated mode of operation of MBR BNR systems is as extended aeration WWTPs (no primary settling and long sludge age). However, the volume reduction compared with equivalent BNR systems with SSTs will not be large (40-60%), but the cost of the membranes can be offset against sludge thickening and stabilisation costs. Moving from a flow unbalanced raw wastewater system to a flow balanced (fq = 1) low (usually settled) wastewater strength system can double the ADWF capacity of the biological reactor, but the design approach of the WWTP changes away from extended aeration to include primary sludge stabilisation. The cost of primary sludge treatment then has to be offset against the savings of the increased WWTP capacity.     

A pilot study on accelerated sludge degradation by a high-concentration membrane bioreactor coupled with sludge pretreatment.

A new sludge treatment process combining a high MLSS membrane bioreactor with sludge pretreatment techniques was studied in pilot-scale experiments. The membrane bioreactor (MBR) was adopted for high efficiency aerobic digestion. The combination of alkaline-ozone treatment of the mixed liquor in the MBR reactor accelerated the biodegradation process by enhancing biodegradability of the sludge. The hydraulic retention time (HRT) of the reactor was set as 3.1 days and the DO level was 1 mg/L on average. After 5 months of operation, the accumulative total solids reduction was more than 70%. Removal efficiency of volatile solids and non-volatile solids were 76% and 54%, respectively. It was found that a considerable portion of the non-volatile solids was dissolved into ions and then flushed out with the effluent. Also, about 41% and 28% of T-N and T-P in the raw sludge were removed although no biological nutrient removal process was adopted. The experiment was run smoothly without significant membrane fouling, even at the relatively high levels of MLSS concentration (11,000-25,000 mg/L). It is concluded that the newly proposed process can significantly increase the sludge reduction efficiency with much shorter retention times.     

Effect of low dosages of powdered activated carbon on membrane bioreactor performance

Previous research has demonstrated that powdered activated carbon (PAC), when applied at very low dosages and long SRTs, reduces membrane fouling in membrane bioreactors (MBRs). This effect was related to the formation of stronger sludge flocs, which are less sensitive to shear. In this contribution the long-term effect of PAC addition was studied by running two parallel MBRs on sewage. To one of these, PAC was dosed and a lower fouling tendency of the sludge was verified, with a 70% longer sustainable filtration time. Low PAC dosages showed additional advantages with regard to oxygen transfer and dewaterability, which may provide savings on operational costs.     

Removal mechanisms of 17β-estradiol and 17α-ethinylestradiol in membrane bioreactors

The fate and behavior of natural and synthetic estrogens in wastewater treatment processes is currently of increasing concern all over the world. In this study, the removal mechanisms of a natural estrogen, 17β-estradiol (E2), and a synthetic estrogen, 17α-ethinylestradiol (EE2) were investigated in membrane bioreactors (MBRs) with and without powdered activated carbon (PAC) addition. The experimental results showed that the average removal rates of E2 and EE2 by the MBR without PAC addition were 89.0 and 70.9%; PAC addition in the MBR increased the removal rate of E2 and EE2 by 3.4 and 15.8%, respectively. The greater impact of PAC dosing on EE2 removal was due to its greater hydrophobic property. Adsorption played a more important role in the removal mechanisms of EE2 than E2. Biodegradation was the dominant mechanism for the removal of E2 and EE2 in MBRs. Unlike their adsorption behavior, the biodegradation rates of both E2 and EE2 were not significantly different between the MBRs with and without PAC addition.     

Treatment of ametryn in wastewater by a hybrid MBR system: a lab-scale study

Agricultural discharge of herbicides to the Great Barrier Reef (GBR) poses significant threat to the marine ecosystem. This study evaluates the performance of a hybrid treatment system consists of a membrane bioreactor (MBR), UV disinfection unit and a granular activated carbon (GAC) column in treating ametryn which is one of the major herbicides in agricultural discharges. While the MBR alone removes only 40% of ametryn at a hydraulic retention time of 7.8 h, the hybrid system removed ametryn to below detection levels.     

Effect of 200 days' sludge retention time on performance of a pilot scale submerged membrane bioreactor for high strength industrial wastewater treatment.

A high strength industrial wastewater was treated using a pilot scale submerged membrane bioreactor (MBR) at a sludge retention time (SRT) of 200 d. The MBR was operated at a high sludge concentration of 20 g/L and a low F/M ratio of 0.11 during 300 d of operation. It was found that the MBR could achieve COD and TOC overall removal efficiencies at more than 99 and 98% TN removal. The turbidity of the permeate was consistently in the range of 0.123 to 0.136 NTU and colour254 absorbance readings varied from 0.0912 to 0.0962 a.u. cm(-1). The sludge concentration was inversely proportional to the hydraulic retention time (HRT), yielded excellent organic removal and extremely low sludge production (0.0016 kgVSS/day).