Study on performance of ultrafiltration membrane-based pretreatment for application to seawater reverse osmosis desalination.

The objective of the work was to study at lab-scale the efficiency of hybrid process- coupling powdered activated carbon (PAC) adsorption or FeCl(3) coagulation and UF- for marine organic matter removal. Regenerated cellulose membrane with 30 kDa and actual seawater from Mediterranean Sea were used. The coagulant was FeCl(3) and adsorbents were two PAC types, with different surface area and pore size distribution. The results showed that PAC adsorption/UF performed higher efficiency in terms of organic removal than FeCl(3) coagulation/UF. Organic matter removal up to 50% was obtained for a PAC dose of 200 mg/L. According to high performance size exclusion chromatography (HP-SEC) analysis, the organics removed by PAC/UF are approximately 10 kDa. Therefore, the effect of PAC adsorption was deeply evaluated in terms of UF membrane fouling rate. The fouling rate was reduced when increasing PAC dose for both PAC types, in particular when PAC with a higher BET surface area and larger fraction of micropores was used. On the other hand, the results showed that UF unit could highly reduce SDI(3) from 26 to 9. The addition of PAC and FeCl(3) to UF allowed a further reduction of SDI(3) from 9 to 4-6.

Fouling and its reversibility in relation to flow properties and module design in aerated hollow fibre modules for membrane bioreactors.

Nowadays, most membrane bioreactors are using membranes submerged in the biomass and aeration in the concentrate compartment to limit or to control fouling. An important issue for the design of modules or membrane bundles in MBRs is to understand how the air/liquid flow is behaving and influencing fouling and its reversibility in relationship to the module properties. This paper focuses on an innovative and very specific process, in which HF membranes are put in a cartridge outside the activated sludge tank and a recycling loop is associated to the cartridge in order to decrease concentration of foulant species at the membrane surface and mass transfer resistance. Recycling operates with a very low liquid velocity in the module (a few cm.s(-1)) which constitutes a specificity of this process in terms of filtration operation. The aim of this study is to characterise two-phase flow and its effects on fouling and fouling reversibility at the scale of a semi-industrial bundle of outside/in hollow fibres, and as a function of bundle properties (packing density, fibre diameter), using specific methods to characterise the flow and fouling effects. Two modules were used showing a different packing density. Filtration was operated at constant permeate flux with clay suspension at 0.65 g.l(-1) in the same hydrodynamic conditions. Fouling kinetics and irreversibility were characterised by an adapted step method, and gas and liquid flows were characterised at global scale by residence time distribution analyses and gas hold-up. Fouling velocities are clearly influenced by gas velocity. The proportion of dead to total volume in the module is mainly affected by the liquid flow velocity and module design. The module with the higher fibre diameter and the lower packing density showed better performances in terms of fouling which was correlated with better flow properties.

Performances of a hybrid adsorption/submerged membrane biological process for toxic waste removal.

This study focuses on a hybrid process, which combines adsorption on powdered activated carbon (PAC), membrane separation using immersed hollow fibers and biological activity. The first part shows that PAC addition in a complex system (containing dissolved molecules and biological particles) can reduce membrane fouling. In that system, DMP removal is function of the activated carbon concentration. Then, respirometric experiments allowed comparison of toxic sensitivity and biological degradation of different bioreactors (membrane bioreactor (MBR), adsorptive membrane bioreactor (PAC-MBR) and classical activated sludge bioreactor (AS)). Results point out that MBR sludge is less sensitive to the toxic than the AS. For high toxic concentration, PAC addition in the MBR decreases rapidly the toxic concentration under the EC50 in the bioreactor, which allows a better biodegradation of the toxic compound. DMP assimilation is completed more rapidly with the PAC-MBR than the MBR.

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).

Mechanisms of action of particles used for fouling mitigation in membrane bioreactors.

Adding chemicals to the biofluid is an option to mitigate membrane fouling in membrane bioreactors. In particular, previous studies have shown that the addition of particles could enhance activated sludge filterability. Nevertheless, the mechanisms responsible for the improved filtration performance when particles are added are still unclear. Two main mechanisms might occur: soluble organic matter adsorption onto the particles and/or cake structure modification. To date, no studies have clearly dissociated the impact of these two phenomena as a method was needed for the in-line characterization of the cake structure during filtration. The objective of this study was thus to apply, for the first time, an optical method for in-situ, non-invasive, characterization of cake structure during filtration of a real biofluid in presence of particles. This method was firstly used to study local cake compressibility during the biofluid filtration. It was found that the first layers of the cake were incompressible whereas the cake appeared to be compressible at global scale. This questions the global scale analysis generally used to study cake compressibility and highlights the interest of coupling local characterization with overall process performance analysis. Secondly, the impact of adding submicronic melamine particles into the biofluid was studied. It appears that particles added into the biofluid strongly influence the cake properties, making it thicker and more permeable. Furthermore, by using liquid chromatography with an organic carbon detector to determine the detailed characteristics of the feed and permeate, it was shown that the modification of cake structure also affected the retention of soluble organic compounds by the membrane and thus the cake composition. Simultaneous use of a method for in-situ characterization of the cake structure with a detailed analysis of the fluid composition and monitoring of the global performance is thus a powerful method for evaluating cake structure and composition and their impact on global process performance. The use of this methodology should allow "cake engineering" to be developed so that cake properties (structure, composition) can be controlled and process performance optimized.

A new method for permeability measurement of hydrophobic membranes in Vacuum Membrane Distillation process.

In this paper, a new method for permeability measurement of hydrophobic membranes used in Vacuum Membrane Distillation, instead of common measurement methods, was proposed. As VMD is a pressure and temperature driven process, the idea of this work is to propose a new water vapour permeability measurement method based on variation of feed temperature at a fixed vacuum pressure. This new method showed a greater stability and simplicity than the existing pressure variation method by not only allowing a wide range of feed temperature (25 °C ÷ 60 °C) to be scanned continuously, but also avoiding fluctuations of the system as observed in the pressure variation test. Permeabilities of two different kinds of hydrophobic membranes were measured by this new method and also by the existing pressure variation test. A comparison between these two methods was also presented to assess the feasibility and applicability of this new method.

A new biosynthetic tracer for the inline measurement of virus retention in membrane processes: part I--Synthesis protocol.

In this study, a new biosynthetic tracer was developed to characterize the virus retention dynamics of membrane systems. This new tracer is a modified bacteriophage obtained by the grafting of enzymatic probes to an MS2 bacteriophage, one of the smallest non-pathogenic bacteria viruses, with an average diameter of about 30 nm. A protocol for the synthesis and purification of this new tracer was developed in this work. The production of this biosynthetic tracer was first qualitatively shown by a chromatographic characterization and an enzymatic test. The average number of probes grafted per phage was then quantified for three batches of tracers made from the same native phage suspension and the same batch of enzymatic probes. This quantification demonstrated the reproducibility of the synthesis protocol developed.

A new biosynthetic tracer for the inline measurement of virus retention in membrane processes: part II. Biochemical and physicochemical characterizations of the new tracer.

In a previous work, a reproducible procedure to produce a new biosynthetic tracer was developed. This new tracer is an MS2 bacteriophage with enzymatic probes grafted on its surface, which can induce enzymatic activity of the tracer. In this paper, the biochemical and physicochemical characteristics of this new tracer are determined. A protocol was developed to determine the specific enzymatic activity kcat(TRACER) of the tracer, which was found to be 2.93±0.78×10(4) min(-1) on average. Physicochemical characterizations of this new tracer showed that it is representative of viruses and may thus be used as a virus surrogate to assess the virus retention of membrane systems inline. Notably, the mean diameter and molecular weight of the tracer were found to be respectively 64.1±0.3 nm and 12,140±3654 kDa, which are within the size and molecular weight ranges of pathogenic viruses carried by water. The tracer surface was also studied and revealed the considerable porosity of the grafted probe layer, with a mean porosity of 88%, which could explain why the zeta potential of the tracers (-14.34±1.66 mV) was nearly the same as that of the native MS2 phages. Finally, a comparison between filtration of the reference microorganism used for membrane performance assessment (the MS2 phage) and the tracer suspensions showed the same filtration behaviour.

Side-stream membrane bioreactors: Influence of stress generated by hydrodynamics on floc structure, supernatant quality and fouling propensity.

This work aims to characterise the impact of hydrodynamics on sludge properties and consequently on fouling mechanisms in side-stream membrane bioreactors (MBRs). Two side-stream processes which generate very different shear stresses are compared, without filtration. This operating mode permits specific quantification of the impact of the external loop (and of induced shear stress) on floc structure/morphology, supernatant quality and fouling propensity. The study shows that low constraints (7 x 10(-3) Pa) generated on submerged side-stream hollow fibre modules have no significant impact on sludge properties. In contrast, high shear stresses (72 Pa) associated with a crossflow configuration induce very significant modifications of the mixed liquor which increases its fouling propensity (measured in a standard filtration cell). A theoretical explanation of the role of turbulence on the floc size distribution is given. Based on a Kolmogorov microscale calculation, it seems possible to predict the mean floc size reached in both filtration systems, for a given shear stress intensity. Disaggregation is characterised by a two-step kinetic: first a short-term breakage attributed to fragmentation and loss of weak strength bonds, and secondly a longer-term breakage probably due to erosion phenomena and removal of high strength bonds. Only the second step induces a significant release and an accumulation of soluble protein-like substances. Soluble organic matter strongly enhances the fouling propensity of the mixed liquor. This seems to be amplified by the concentration of protein-like substances. The importance of considering the protein and carbohydrate content as well as floc size is also pointed out in the paper.

Bactericidal properties of peracetic acid and hydrogen peroxide, alone and in combination, and chlorine and formaldehyde against bacterial water strains.

The bactericidal properties of peracetic acid, hydrogen peroxide, chlorine, and formaldehyde were compared in vitro using a rapid micromethod. A combination of peracetic acid and hydrogen peroxide was also tested to assess interactions. The activities of these agents, which are widely used as disinfectants, were evaluated against water isolates and culture collection strains. Peracetic acid and chlorine exhibited an excellent antimicrobial activity, with a relatively rapid destruction of 10(5) bacteria/mL. The time-dependent bactericidal activities of hydrogen peroxide and formaldehyde were the lowest. The combination of peracetic acid and hydrogen peroxide, tested by a checkerboard micromethod, was found to be synergistic. The minimal bactericidal concentration was established in terms of time for a given mixture of peracetic acid and hydrogen peroxide. Determination of bactericidal concentrations showed that synergy was maintained with increasing contact time. Concentrations for minimal times of treatment by chemicals that provided interesting activities in vitro were tested for disinfection of ultrafiltration membranes. The bactericidal activities of peroxygen compounds were confirmed and synergism was maintained in working conditions. Chlorine showed a loss of efficacy when used on membranes.

Sporocidal properties of peracetic acid and hydrogen peroxide, alone and in combination, in comparison with chlorine and formaldehyde for ultrafiltration membrane disinfection.

The sporocidal properties of peracetic acid, hydrogen peroxide, chlorine, and formaldehyde were compared in vitro using a dilution-neutralization micromethod. A combination of peracetic acid and hydrogen peroxide was also tested to assess their interactions. The activities of these agents, which are widely used as disinfectants, were evaluated against Bacillus spore isolates found on stored membranes and collection cultures. Peracetic acid and chlorine exhibited an excellent antimicrobial activity, with a destruction of 10(5) spores/mL after 5 min of contact. Generally the effects of the biocides tested were time dependent. The sporocidal activities of hydrogen peroxide and formaldehyde were the lowest. The combination of peracetic acid and hydrogen peroxide, tested by a checkerboard micromethod, was found to be synergistic. The minimal sporocidal concentration (MSC) was established in terms of time for each biocide. The lowest MSC values for peracetic acid, hydrogen peroxide, chlorine, and formaldehyde were 168-336 ppm (1-2 h of contact), 5625-11250 ppm (5-7 h), 168-336 ppm (2-3 h), and 1875-3750 ppm (5-30 min), respectively. The MSC of a biocide combination of peracetic acid and hydrogen peroxide showed that synergy was maintained with increasing contact time and that the MSC could be reduced by two to eight times when compared with those of the biocides alone. Optimal concentrations and contact times of those chemicals that were promising in vitro were then tested for their ability to disinfect ultrafiltration membranes. The sporocidal activities of peroxide compounds and chlorine were confirmed and the synergism between peracetic acid and hydrogen peroxide was also maintained.(ABSTRACT TRUNCATED AT 250 WORDS)