Prevention of Biofouling in Industrial RO Systems: Experiences with Peracetic Acid W.B.P. van den Broek*, M.J. Boorsma **, H. Huiting***, M.G. Dusamos **** and S. van Agtmaal* * Evides Industriewater, Evides B.V., PO Box 4472, 3006 AL Rotterdam, The Netherlands (E-mail: [email protected]) ** WLN, PO Box 26, 9470 AA Zuidlaren, The Netherlands (E-mail: [email protected]) *** KWR Industry & Water, KWR Watercycle Research Institute, PO Box 1072, 3430 BB Nieuwegein, The Netherlands (E-mail: [email protected]) **** JohnsonDiversey B.V., PO Box 40441, 3504AE Utrecht, The Netherlands (E-mail: [email protected]) Abstract: Biofouling is the major fouling type occurring in reverse osmosis (RO) plants treating surface water or effluent from a waste water treatment plant. Severe biofouling can result in operational problems, higher energy and chemical consumption and premature membrane replacement. There are different methods to control biofouling. One method is removal of nutrients in the pre-treatment of the membrane filtration plant, another method is periodic removal of biofouling by chemical cleanings or the use of chemicals to prevent biological growth in the RO systems. In this paper the results of experiments with peracetic acid on three different full scale plants are presented. Two of the plants are operated by Evides Industriewater, the third one by Bètawater, a subsidiary company for industry water of Waterleidingmaatschappij Drenthe (WMD). One of the main outcomes is that biofouling can be controlled fully on reverse osmosis (RO) plants with the applied method with a peracetic acid based product (Divosan Activ). If the proper measures are taken to avoid oxidation damage due to transition metals, this method with the environmental friendly product results in a stable process and savings by a significantly reduced CIP interval. Keywords Biofouling, Peracetic Acid, Reverse Osmosis, Prevention, Biofouling Control, Pre-treatment, Operational Experience. INTRODUCTION A major problem in RO systems is fouling of the membrane elements. Severe fouling will cause serious operational problems, like loss of productivity, increased pressure drop, loss of retention, frequent chemical cleanings and premature RO element and cartridge filter replacement. All these problems result in higher operation costs. The major fouling mechanisms of RO systems are biofouling, scaling, inorganic colloids and organic fouling. Different types of fouling can occur simultaneously, influencing each other. In practice it is difficult to find out which fouling occurs first and which fouling is the result from the initial fouling. Biofouling is the most occurring fouling in reverse osmosis systems for desalination (Khedr, 2000), specifically in systems with surface water or effluent from Waste Water Treatment Plants (WWTP) as raw water source. These water sources contain Natural Organic Matter (NOM). Part of the NOM is present as low concentration easily biodegradable compounds, which can be used by micro organisms as a carbon source for their growth and reproduction. In the presence of easily assimilable carbon and sufficient nutrients (typical Phosphor and Nitrogen containing sources) biological growth will occur as a biofilm on all kind of surfaces. Excessive biological growth will result in biofouling: accumulation of biomass on a surface by growth and/or deposition to a level causing operational problems (Vrouwenvelder, 2001). Water Practice & Technology Vol 5 No 2 © IWA Publishing 2010 doi: 10.2166/WPT.2010.042 Controlling Biofouling in membrane filtration systems Based on the above considerations, controlling biofouling is considered to be the major challenge when operating a membrane filtration installation. There are different options to control biofouling in membrane filtration installations. An option often applied for industrial membrane applications is curative; the biofouling is removed by chemical cleanings via the Cleaning In Place (CIP) method. In industrial membrane applications with little biofouling the CIP is applied as generic cleaning method typically once each or every second month. The CIP systems for industrial membrane applications are commonly designed for this usage frequency and not fully automated. In installations with severe biofouling a significantly increased CIP frequency is required (e.g. twice a week). On sites with multiple RO trains this is not a practical solution for the operational staff. Another option is the prevention of the biofouling. This can be achieved by preventing the growth by removal of the nutrients and easily assimilable carbon in an extensive pre-treatment system or by inhibiting the growth by the use of (biocidal) chemicals. Usable pre-treatment processes to reduce the biofouling are processes that reduce the compounds that micro organisms need to grow on. As a result the biofouling in the adjacent membrane system is strongly reduced. Examples of these pre-treatment processes are: • Flocculation/coagulation/sedimentation and filtration • (Biological) activated carbon filtration • Denutritor technology (Jansen, 2007) • Scavenging with ion exchange resins In many recent RO installations the pre-treatment contains an Ultrafiltration system. This pre-treatment is very effective in removal of particles, suspended matter and colloids, but not sufficient to remove low molecular NOM or ammonium and thus not sufficient to prevent biofouling growth in piping, storage tanks and downstream RO system. The use of chemicals to control biofouling can be based on either the principle to prevent or limit the growth of micro organism with non oxidising chemicals or by destroying the biofouling with weak oxidizing agents. In general the application of strong oxidants is not recommended because of the poor chemical resistance of the reverse osmosis membranes for those chemicals. However, under specific conditions some of these chemicals can be applied. Possible chemicals or combinations of chemicals to control biofouling are: non oxidizing: • DBNPA (2,2-dibromo-3-nitrilopropionamide) • Isothiazolones • Sodium bisulphite (reducing) mildly oxidizing: • Monochloramines strong oxidizing: • Peracetic acid (PAA) and hydrogen peroxide • Chlorine dioxide • Hydrogen peroxide silver blend 2 PERACETIC ACID Peracetic acid is an unstable molecule formed by the reaction of acetic acid with hydrogen peroxide at a low pH. CH3COOH + H2O2 ÅÆ CH3COOOH + H2O The oxidation potential of PAA (1.81 eV) lies between ozone (2.07 eV) and chlorine dioxide (1.57) (OMRI, 2008). The oxidative effect is besides the oxidation potential dependent on the applied concentration, the dissociation state (pH dependent), temperature and (cumulative) contact time. Although PAA has a considerable oxidation potential and herewith the potential to degrade the RO membrane, in the recommended concentrations and environment it is expected to be insufficient to attack most polyamide thin-film RO membranes. This expectation is based on the allowance stated by the membrane manufacturers for the use of PAA at certain concentrations and under certain conditions, as shown in Table 1. Table 1: Guidelines for the use of peracetic acid or hydrogen peroxide Maximum concentrations DOW Technical Manual 2005 0.2% H2O2 Hydranautics TSB110.08 2006 <0.2% H2O2 + PAA Maximum temperature Compatibility <25°C 0.5%, 96 h <25°C Other mentioned aspects remove Fe CSM Technical Manual 2006 0.2% H2O2 + 400 mg/l PAA <25°C no transition metals transition metals can (Fe, Mn) in feed cause damage water The PAA used in the experiments described in this article is the commercially available product Divosan Activ (JohnsonDiversey), this is a stabilised mixture of hydrogen peroxide, acetic acid and peracetic acid. PAA based products are used since decades in Food & Beverage and Laundry applications as halogen free oxidiser, bleaching agent and/or disinfectant. In many applications it is used as an alternative to hypochlorite. The PAA based product used in the tests described in this paper is used over many years in Dairy (RO) membrane filtration plants in case disinfection is required. Advantage of PAA based products in industrial RO membrane filtration systems is the effectiveness and rapid action at low to moderate temperatures (5 – 40 ºC), the very good rinsability, and the effectiveness in systems with some (mineral or organic) fouling. To minimise potential impact on the membranes and operation costs, intermittent dosage is an interesting concept compared to the continuous application of a biofouling control agent. This also allows to apply a different water source during the application. Recently the improved effectiveness of the intermittent application of biocides (in general) versus continuous application has been reported by a model study (Szomolay, 2006). PAA based products need to be handled with care by trained staff only. Operational safety is to be ensured by using the proper chemical storage, handling and dosing systems. The application has to be applied according the valid local legislation. As of the degassing nature of PAA, low dosages and long dosing idle periods, operational reliability requires the usage of a suitable dosing system. PAA is a halogen free oxidiser, this prevents the formation of halogenated organic compounds or trihalogen compounds (THC) as with halogen comprising oxidation agents. PAA will break down 3 via acetic acid and hydrogen peroxide to the environmentally safe and natural compounds carbon dioxide, oxygen and water. In general, oxidative agents used for cleaning polyamide RO membranes can cause oxidative membrane degradation. Membrane manufacturers give guidelines for the use of these chemicals. In table 1 the guidelines of the manufacturers of the membranes used in the described experiments are given. The guidelines of these manufacturers are almost the same. The DOW Technical manual mentions only H2O2, Hydranautics only the mixture with PAA (without exact concentration) and CSM the complete mixture with concentrations. Temperature, pH and the presence of transition metals are critical aspects when using PAA. Therefore measures should be taken to prevent transition metals, more specifically manganese and iron, presence during the application of PAA on polymeric RO membranes. The concentrations of H2O2 used in the described experiments are 25-50 times lower than the guidelines in table 1. The described experiments are all executed with Divosan Activ with a ratio PAA: H2O2 being 5.5:24. Usage of products with a different PAA: H2O2 ratio can influence the results. OPERATIONAL EXPERIENCES IN INDUSTRIAL RO PLANTS Evides Industriewater owns and operates a number of industrial membrane filtration plants, that have (had) problems with biofouling. Implementing an additional pretreatment in the existing plants to prevent the biofouling would require large investments and retrofits of the plants. Therefore Evides Industriewater decided to research the control of biofouling by the application of chemicals. For the same reason WLN and Bètawater, a subsidiary company for industry water of N.V. Waterleidingmaatschappij Drenthe (WMD) investigated this subject. The experiments with PAA (Divosan Active) were tested in cooperation with JohnsonDiversey, the supplier of this product. Tests were carried out during the normal operation of the membrane filtration plants. Demin water plant Baanhoek At the industrial water plant Baanhoek surface water (Biesboschwater) is treated with ultrafiltration – antiscalant dosing – reverse osmosis – degasifier – mixed bed ion exchange to demin water. Membranes in this plant are from Dow FilmTec. Due to biofouling the RO systems had to be chemically cleaned once a week in summer time, resulting in a stressed operation of the plant. To control biofouling the following chemicals have been tested: • Intermittent dosage of peracetic acid /hydrogen peroxide • Off line dosage of chlorine dioxide • Off line shock treatment with sodium bisulphite In this paper only the results of the test with PAA are illustrated. The feed water for the RO is ultrafiltrated surface water from the Biesbosch reservoirs. Before the UF 0.5 mg/l Fe is dosed as flocculant, but the removal of this iron is very good. (Table 2) Just before the RO 3 mg/l antiscalant (Permatreat 191T) is dosed. This antiscalant prevents also iron fouling on the membrane. Normally the CIP frequency in winter and early spring is low. In April the pressure drop of the 1st stage RO membranes starts to increase, resulting in a higher cleaning frequency. The intermittent dosage of PAA was started early April 2006 just after a CIP of the RO trains. 4 Table 2: Water quality feed water RO Temperature (°C) Iron (mg/L) TOC (mg/L C) pH Min 3.0 <0.005 3.0 Avg 13 0.005 3.3 7.5 Max 24 0.016 3.5 Tests were performed on one line and another line was operated under normal condition to compare the efficiency. The PAA was dosed inline before the cartridge filters in a concentration of 10-15 mg/l for 5 min every 3 hours. There was almost no consumption of PAA during passage of the RO-modules. The concentration of PAA in the permeate was less than in de concentrate but still about 10 mg/l was found in the permeate. The results are shown in figure 1. The normalized pressure drop of the RO train without the dosage of PAA (blue dots) starts to increase and therefore requiring chemical cleanings. With warmer feed water in early summer the pressure drop increases more rapidly. The pressure drop of the RO train with the PAA dosage (red dots) remains low. 4.5 Normalized Pressure Drop [bar] 4.0 Dosage stopped June 21, 2006 RO without Peracetic acid RO with Peracetic acid 3.5 3.0 2.5 2.0 1.5 1.0 0.5 6/ 30 /2 00 6 6/ 20 /2 00 6 6/ 10 /2 00 6 5/ 31 /2 00 6 5/ 21 /2 00 6 5/ 11 /2 00 6 5/ 1/ 20 06 4/ 21 /2 00 6 4/ 11 /2 00 6 4/ 1/ 20 06 0.0 Date Figure 1: Efficiency of peracetic acid/hydrogen peroxide on biofouling control The normalized pressure drop is calculated as follows: NPD = Tcf x Qcf x dP where Tcf = (viscosity at T=25°C/viscosity at T=T)^N Qcf= (Q ref/Qavg)^M Tcf = Temperature correction factor Qcf = Flow correction factor Qref= Reference flow dP= differential pressure (Pconcentrate –Pfeed) M and N are membrane specific parameters 5 June 21, 2006 the intermittent dosage of peracetic acid/hydrogen peroxide had to be stopped due to a permeate quality problem. In the period thereafter the pressure drop of that RO system also started to increase rapidly with the same rate as the other unit. In the two and a half months period the RO system without the application of PAA had to be cleaned 9 times, while the train with PAA did not require any cleaning. Also the cartridge filters of the RO without PAA had to be changed several times per month while the system with PAA didn’t need replacements. During the dosage of PAA the normalized salt passage (NSP) dropped slightly as can be seen in Figure 2. The decline of the NSP indicates that there was no degradation of the RO membrane during this experiment. NSP RO with PAA 4,0 Dosage stopped June 21, 2006 3,5 Normalized Salt Passage [%] 3,0 2,5 2,0 1,5 1,0 0,5 Date Figure 2: Normalized Salt Passage RO with PAA The normalized salt passage is calculated as follows: NSP = ECpas x Tcf,sp x Qcf,sp ECpas = 100 x ECp /(ECf x ln(1/(1-R/100))/(R/100)) Tcf,sp = e^(U x (1/(Tf + 273,15)-1/(273,15+25°C)) R =100 x Qp/Qf Qcf,sp = Qp/Qp,ref where ECpas = passage of electrical conductivity ECp = electrical conductivity permeate ECf = electrical conductivity feed water Tcf,sp = temperature correction factor for the salt passage Tf = temperature feed water U = membrane specific parameter Qcf,sp = flow correction factor for the salt passage Qp = flow permeate Qf = flow feed water Qp,ref = reference flow permeate R = recovery 6 710 -2 00 6 630 -2 00 6 20 06 620 - 610 -2 00 6 531 -2 00 6 521 -2 00 6 511 -2 00 6 5120 06 20 06 421 - 411 -2 00 6 4120 06 0,0 Demin water plant Sas van Gent The raw water source for the plant in Sas van Gent is effluent from an industrial waste water treatment plant at a starch producing plant. The treatment consists of an inline flocculation with iron, dual media filtration, ultrafiltration, antiscalant dosing, first pass RO system, degasifiers and a second pass RO system. In times when the effluent water can not be used due to quality issues drinking water is used as feed water for the RO. The water treatment plant produces demineralised water for the starch producing plant. Initially (December 2006 – February 2007) the dosing of PAA was done at one RO system (RO1A) on already fouled ESPA2 membranes (from Hydranautics) with a very high pressure drop. The other RO, with the same fouled membranes, was kept as a reference. The dosage was 18 mg/l inline for 5 minutes every 3 to 6 hours with the permeate to waste. In a month time the normalized pressure drop (NPD) of the ROsystem (1st array) with PAA dosing was down by 0.4 bar while the NPD of the reference system was up by 0.5 bar. Meanwhile the mass transfer coefficient (MTC) and NSP did not change in either system. Due to these promising results after two months a PAA dosing was started on the other RO line too. In the following months the pressure drop could not be kept stable (also not with an increased dosing frequency of every 4 hours) and in June/July 2007 membranes for both RO lines were replaced by new membranes: Dow FilmTec for RO1A and Saehan membranes for RO1B. Table 3: Water quality feed water RO (when effluent is used) Temperature (°C) Iron (mg/L) TOC (mg/L C) pH Min 25 0.05 15 Avg 30 0.16 20 7.2 Max 35 0.32 25 When effluent is used as source water the temperature is high and also the iron concentration (permeate of the UF-system) is high due to colloidal particles not held back by the UF-system. The required antiscalant level for water with, - besides ionic iron -, also colloidal iron is unclear and can be a cause for iron deposit formation on the membranes. These are two risk factors for damaging the membranes. For minimising this risk the dosing frequency was lowered to every 6 hours and from November 2007 to every 24 hours with effluent and no dosing with drinking water. Also the dosage was adjusted to obtain a concentration of 1-2 mg/l of PAA in the concentrate after the 1st array. The alternative for preventing the iron risk is to dose the PAA in a flush with demin water. Technically this was more difficult to establish and this would result in more water loss and downtime of the system. Furthermore it would still be possible that colloidal iron deposit is present on the membrane surface. This can be removed only periodically with a proper CIP and can not be prevented by applying an antiscalant. Figure 3 shows that the NPD is kept stable for the whole period of dosing (more than 8 months) with about every 6 weeks a preventive CIP. In November 2007 an evaluation was made of the first dosing period. At that time it became clear that there was a steady increase in NSP (figure 4). The yellow line is the temperature and an indicator for the type of water source: above 22°C it is effluent else it is drinking water. Then, the dosing frequency was lowered strongly. But as the graph shows, even in the period of decreased dosing frequency the NSP looks to increase further. Only after stopping the dosage the NSP seems to stabilize or even slightly to decrease. 7 NPD (Normalised Pressure Drop) RO1B NPD array 1 NPD array 2 CIP Temperature Saehane RE 8040FE (7-25-2007) 4,00 dosing every 24 h (effluent); no dosing on drinking water dosing every 6 h (effluent and drinking water 40 35 Normalised Pressure Drop [Bar] 25 20 2,00 15 Temperature (°C) 30 3,00 10 1,00 5 0 716 -2 00 8 527 -2 00 8 -2 00 8 47 217 -2 00 8 12 -2 920 07 11 -9 -2 00 7 920 -2 00 7 81 -2 00 7 0,00 Date Figure 3: Normalized pressure drop RO1B demin water plant Sas van Gent NSP (Normalised Salt Passage) RO1B Saehane RE 8040FE CIP 2,00 20 1,50 15 1,00 10 0,50 5 0,00 0 716 -2 00 8 25 527 -2 00 8 2,50 4720 08 30 217 -2 00 8 3,00 12 -2 920 07 35 11 -9 -2 00 7 3,50 920 -2 00 7 40 Temperature (°C) Temperature 4,00 8120 07 Normalised Salt Passage [%] EGV passage dosing every 24 h (effluent); no dosing on drinking water dosing every 6 h (effluent and drinking water Date Figure 4: Normalized Salt Passage RO1B demin water plant Sas van Gent The other RO line with Dow FilmTec membranes operated under the same conditions showed similar results. This increase of the NSP seems to be the result of the degradation of the RO membrane due to the combination of dosing PAA, relatively high temperature of the water and the presence of iron in the feedwater. In April 2008 the dosing of PAA was ended because of the risk of too high salt passage. Now a periodic (once every 1-2 days) conservation with sodium bisulphite is applied with a concentration of 0.9%. 8 Demin water plant Klazienaveen At the site in Klazienaveen (in the province of Drenthe, The Netherlands) boiler feed water is produced from surface water with ultrafiltration and reverse osmosis (with antiscalant dose). Since the surface water contains high levels of organic matter a coagulation with poly aluminium chloride (PAC) and continuous sand filtration is used as pre-treatment. Experiments with PAA and DBNPA carried out on this plant were technologically supported by WLN and financially by InnoWATER (a Dutch subsidy scheme for innovative water technology). In this paper only the results of the test with PAA are illustrated. Table 4: Water quality feed water RO Temperature (°C) Iron (mg/L) Manganese (mg/L) DOC (mg/L C) pH Min 1.0 < 0.005 < 0.005 3.0 Avg 12 0.018 0.12 8.1 6.8 Max 25 0.13 0.34 14.2 The RO system consists of 3 lines (RO1, RO2 and RO3); RO1 contains Hydranautics ESPA2-membranes, intensively used since 2004; RO2 new ESPA2membranes (March 2007) and RO3 new Trisep LF membranes (March 2007). The dosage of PAA was only applied to RO1. The dosage took place in the period from 30th May till 13th November 2007 and as from April 2008. Historically, only during this period with a higher feed water temperature biofouling occurs. Before the start of the experiment the feed piping is internally hydraulically cleaned and also the RO membranes were intensively cleaned by CIP to remove any transition metals from the membranes in case these would be present as surface foulant. PAA was dosed during 5 minutes in RO-permeate during a flush (total flush time: 15 minutes). RO permeate is used to ensure transition metal free water. At normal operation the antiscalant is used to avoid any new deposits from transition metals. During 2007 10 mg/l PAA (first few weeks 5 mg/l) was dosed every 3 to 4 hours. In April 2008 the dosing of PAA was started again, now with a six hours interval. Since the beginning of July 2008 the dosing frequency is further reduced to three times a day. In figure 5 the normalized pressure drop is shown for the 3 different RO-lines. The purple line is from RO1 with the PAA-dosing, the brown line is from RO2 and the green line from RO3. As can be seen the purple line is stable in time. Since the experiment on RO1 started (May 2007) until July 2008, RO1 has been cleaned 4 times preventively whereas the reference (RO2) had to be cleaned 14 times (together with replacements of cartridge filters) curatively due to the increased NPD. Figure 6 shows that the NSP of the 1st stage of RO1 (purple line) is stable during the period of dosing (June-October 2007 and since April 2008). The reference RO2 (brown line) is slightly decreasing probably due to fouling of the membranes. No negative effect has been observed on the salt passage using this dosing protocol on these membranes. In the first weeks of dosing PAA (5 mg/l) there was no residual PAA found after the cartridge filter. However even then there was a positive effect on the development of the NPD. The benefits of the PAA usage in this experiment (1 RO line over a period of 14-15 months) are the saving of cartridge filters, 20 man-days (often unplanned and during holiday season) to execute RO CIP cleanings, less usage of CIP chemicals and waste, energy saving as of reduced operational pressure and possibly longer life time of the membranes (as a result of little to none biofouling growth and 9 less chemical cleaning). Dosing during a flush with RO-permeate has a small disadvantage as well, that is loss of product and production time. In general it resulted in a far more stable and thus better manageable process. Figure 5: Normalized pressure drop first stage RO’s Klazienaveen NSP (Normalised Salt Passage) 1st stages RO 1, 2 en 3 4 No PAA dosing PAA Dosing PAA on RO 1; every 3 - 4 h No PAA dosing PAA Dosing PAA on RO 1; every 6 - 8 h 3.5 3 EC passage [%] 2.5 2 1.5 1 0.5 0 Mar-07 May-07 Jul-07 Sep-07 Nov-07 Jan-08 Mar-08 Date Tref: 20 °C RO1 1e trap RO2 1e trap Figure 6: Normalized Salt Passage first stage RO’s Klazienaveen 10 RO3 1e trap May-08 Jul-08 The positive results have led to the extension of this experiment this year (2008) with a lower frequency of once every 6 to 8 hours. The results are obtained with 3 year old membranes and a point of research is the effect (salt passage) on new membranes after an initial period of operation without the usage of PAA to allow to rinse out any residual (production) material. The results of these three cases show that the use of PAA for biofouling control is possible (without negative side effects) under specific conditions. The increase of the NSP at the Sas van Gent plant can be the result of the high temperature in combination with the iron present in the feedwater (and maybe also on the membranes). These are also the restrictions made by the membrane manufacturers (see table 1) for using PAA. It seems that these restrictions also have to be applied when using PAA in a periodic inline dosing at a low concentration. CONCLUSIONS The following conclusions can be drawn. • periodic (intermittent) inline dosing of low concentration of PAA (Divosan Active) appeared to be very effective in preventing biofouling of RO membranes • part of the PAA (and H2O2) will be found in the permeate when the RO is online during dosage and possible restrictions regarding to following treatment steps or application of the demin water have to be taken into account • inline dosage of PAA on iron containing water (0.2 mg/l) with a temperature of about 30°C on new membranes can result in an increased salt passage within a few months • the damaging effect of the presence of iron (and/or manganese) can be effectively minimized by a proper and regularly executed preventive RO cleaning scheme, dosing the PAA in a flush with demin water and applying an antiscalant as required by the water specifications. References CSM Technical Manual (2006), 91,11. Dow Liquid Separations FilmTec Reverse Osmosis Membranes technical manual (2005), 133-134. Hydranautics Technical Service Bulletin (2006) TSB110.08, 4. Jansen, A.E. (2007) Tecnología de tratamiento del agua en procesos industriales. Expo Agua, Buenos Aires, Argentina. Khedr, M. (2000) Membrane fouling problems in reverse-osmosis desalination applications. Desalination and Water Reuse Quarterly Volume 10/ no. 3, 8–17. OMRI (2000), Peracetic Acid, NOSB TAP Materials Database Compiled by OMRI, www.omri.org/peracetic_acid3.pdf (accessed 11 July 08) Szomolay, B. (2006), “Analysis and control of a biofilm disinfection model”, Dissertation, Montana State University, Bozeman, Montana Vrouwenvelder, J.S. and Kooij, D. van der (2001) Diagnosis, prediction and prevention of biofouling in NF and RO membranes. Desalination 139, 65-71. 11
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