DESUINATION

ELSEVIER
Desalination 13 1 (2000) l-1 6

An outstanding feat of modem technology: the Mery-sur-Oise Nanofiltration Treatment Plant (340,000 ml/d)
Claire Ventresquea*, Vakrie Gisclon, Guy Bablon, Gkrard Chagneaub
Vivendi/G&&ale des Eaux, Quartier Valmy, 32, Place Ronde. 92982 Paris la Dbfense, France Tel. + 33 (I) 55 23 43 73; Fax + 33 (I) 55 23 47 19; email: claire.ventresque@generale-des-eaux.net Syndicat des Eaux d Ze de France, 131, rue du Bat, 75007 Paris, France Tel. + 33 (I) 53 45 42 12; Fax + 33 (I) 53 45 42 69; email: g.chagneau@sed$com Received 26 June 2000; accepted 3 July 2000

Abstract
The paper presents the new membrane plant built by the Syndicat des Eaux dIle de France(SEDIF) in Merysur-Oise. The drinking water plant is able to produce a maximum of 340,000 m3/d of water (90 MGD) for the North Paris Region. A facility with membrane for 140,000 m3/d (37 MGD) is operated in parallel to the existing conventional plant. The commissioning of the membrane plant took place in 1999 and the first thousand cubic meters of water were provided to the distribution system on September 22, 1999. The paper describes how the 9,120 membrane elements were control-checked before commissioning, and how the integrity of the membrane system has been secured. It emphasises the capability of the pre-treatment to provide good quality water in order to control the fouling of the membranes. Keywords:

Nanofiltration; Large-scale membrane plant; Integrity; Sulphate monitoring; Fouling

1. Introduction Located in the north suburbs of Paris, the M&y-sur-Oise treatment plant is the smallest of the three facilities owned by the Syndicat des Eaux dIle de France (SEDTF). The advanced treatment implemented in all three facilities,

*Corresponding author.

which include ozone and activated carbon, has become insufficient for treating the highly polluted water of the Oise River. The M&y-surOise facility, more and more often, experienced inability to remove organics leading to the necessity of decreasing production capacity and lately to stops of the process as a precaution, the other plants of the SEDIF being called up to provide the water to consumers. The concern was to insure that the TKMs would not develop

Presented at the Conference on Membranes in Drinking and Industrial Water Production, Paris, France, 3-6 October 2000 International Water Association, European Desalination Society, American Water Works Association, Japan Waterworks Association 001 l-9164/00!& See f?ont matter 0 2000 Elsevier Science B.V. All rights reserved
PII:SOOll-9164(00)00096-5

C. Ventresque

et al. ,Desalination

131 (2000) l-16

in the distribution system due to high TOC values at the outlet of the plant. As a rule, the plant had to be shut down when the TOC was greater than 2 mg/L. Faced with this problem the SEDIF decided to implement membrane process on Met-y-sur-Oise site [I ,2,3]. The characteristics of the membrane have been defined so that the TOC would fulfil the 2 mg/L requirement and the passage of calcium and bicarbonate would be sufficient in order to lessen the costs of chemicals. During 1999 the new membrane facility was progressively brought into service and in September 1999 water filtered with membrane was supplied for the first time to about 800,000 inhabitants of the region north of lie de France. It was an ambitious project, the realisation of which necessitated numerous innovations. The plant is automated to maximum; the station supervisors control more than 1000 synoptics. There are more than 450 sensors on line, as well as optic fibre connections, etc. As for the cleaning in place, each membrane unit is equipped with pressure, flow and conductivity sensors. Thus, calculators are able to know at any given time if a membrane unit is clean or fouled. If a membrane unit needs to be cleaned, notice is given to the operator who triggers the cleaning procedure or decides to change the recipe. The operator has various recipes at his disposal but he also may decide to apply a recipe of his own (e.g. he may choose to increase the concentration of a cleaning solution or the soaking time). This new recipe is then stored in the computer for further usage. When the cleaning is over, a report is edited which gives, among others, the efficiency and the cost of the cleaning. It is not possible to describe all the innovations, or all the results concerning the membranes - their efficacy vis&vis organic matter, cleaning of membranes. The aim of the present article is essentially to bring together several important points which have appeared over the course of this project and which relate directly to

the subject of water: Performances of the pretreatment set-up to ensure, amongst other, that the quality of the water that feeds the membranes will prevent fouling. The procedures undertaken to control-check the purchase of 9,120 membrane elements. The installing of the membranes and the control checking of the systems integrity as regards bacteriological risks. First results on the quality of the permeate for the period of September 1999-May 2000.

2. Description

of the processes

The new membrane facility is used simultaneously with the conventional biological The membrane facility operates facility. 24 h/24 h at a maximum output of 140,000 m/d. The conventional system produces a minimum output of 30,000 m/d, except in periods of heavy demand during which its contribution can be increased. Membrane filtration is intended to work uninterruptedly because interruptions waste water (for rinsing the concentrate side of the membranes) and because stops must be limited in time (24 to 48 h) in order to minimise risks of biofouling. The scheme of the facilities is presented in Fig. I. There are four main stages for the membrane facility.

2.1. Pre-treatment Pre-treatment enables filtered water to be produced and stored in the intermediary storage tanks. The first stage is an ACTIFLO [4] (weighted floes settler). Sulphuric acid is added at the beginning of the pre-treatment to maintain a pH of about 7 in order that the quantity of aluminium is as low as possible in the water that feeds the membranes thus preventing scaling. The coagulant used is a poly-aluminium chloride

C. Ventresque et al. /Desalination 131 (2000) I-16

Mery-sur-Oise
A - Actiflo clarifiers B - Ozone contact basins C - Coagulant flash mixers i
MEMBRANE PROCESS

Drinking Water Treatment Plant

D - Dual layer filters E - Intermediate tank F - Low pressure pump G - Cartridge prefilters H - High pressure pumps I - Nanofiltration skids E FG,H I ,J
J - UV reactor

K - Mixing K

B,C

10

11

12

13

1 - Water Intake 2 - Raw water storage 3 - Intake tank

6 - Sedimentation tanks 7 - Sandfilters 6 - Ozone contact basins

11 - Biological activated carbon filters 12 - Chlorine contact reservoir 13 - Storage reservoir - Pumping station

4 - Flash mixers 5 - Flocculators

9 - Intermediate tanks
10 - Pumps

Fig. 1. Process scheme of the new membrane facility of Mery-sur-Oise, Membrane process (Train 2) and biological process (Train 1).

and the polyelectrolyte

is an anionic

poly-

electrolyte. The settled water to 1 mg0JL and, after the 5 g/m3 of coagulant, the water dual layer filters composed sand.

is ozonated at 0.5 addition of about is filtered through of anthracite and

2.2. Conditioning

of the water before mem-

brane process
Conditioning consists of the addition of an antiscalant and pre-filtering through cartridges. The antiscalant Hypersperse AF 2001 is

added at about 2 mg,lL. The dosage remains unchanged throughout the year. Pre-filtration is achieved by 8 pre-filters* with an absolute filtration rate of 6 urn. These prefilters function in parallel, each treating 870 m3/h of water. The pre-filters and the cartridges of which they are constituted are designed to be automatically regenerated on site, in order to get rid of the replacing of disposable cartridges (there are 3,280 60cartridges3 in the prefiltration unit). Each pre-filter is backwashed by a contra-current of water every 24 to 36 h * Pall France. 3, rue des Gaudines, Boite Postale no 5253,

Hypersperse AF200 by BetzDearbom

78 175 Saint Germain en Laye, France 3 Septra from Pall France

C. Ventresgue et al. /Desalination 131 (2000) I-16

depending on the particle content of the water at entry. To ensure this backwash, a pre-filtered water reserve of about 3 m3 - situated in the top part of each pre-filter - is forced through the cartridges at high speed by pressurised air (5 bars). This backwashing process insures the elimination of the cake. In any case, the filtering cartridges loss of efficiency after backwashings increases measurably over the course of time, pointing to progressive incrustation. To correct this phenomenon, an automatic chemical regeneration of the pre-filters is activated approximately every 20 d. Thanks to this procedure the life expectancy of the filtering cartridges is extended to a minimum of five years.

stage feeds the following stage. Hydraulic productivity is held steady at 85% by a regulating valve which is placed on the third stage concentrate. The permeates from the stages are gathered together, then pass into the degassing towers.

2.4. Post-treatment Post-treatment comprises degassing towers, UV disinfection and mixing of nanofiltered water with biologically filtered water. pH adjustment with soda and slight chlorination are provided before the water is fed to the distribution system. From the degassing towers situated on the roof of the membrane building, the water flows by gravity.

2.3. Refining Refining includes 8 units of membranes. A connected equipment Cleaning in place (CIP) is controlled automatically. It allows cleaning of the lines of membranes without need of intervention by the personnel. After pre-filtering, the water is divided into 8 parallel pressurised units, each comprising a high pressure pump, a nanofiltration unit and a degassing tower. The pressure tubes, connecting pipes and membrane element assembly and preservation is under the expertise of OTV4. The eight high pressure pumps (5-15 bars) ensure a constant flow of 860 m/h whatever the water temperature or membrane fouling. Each membrane unit contains 1,140 membrane elements NF200B-400 These membranes were chosen for their capacity to reject pesticides and organic matter [5] while allowing calcium and bicarbonates to pass. The nanofiltration units are arranged in 3 stages of 648/324/168 membrane elements respectively. The concentrate of one

3. Materials

and methods

3. I. Bacteriological

measurements

Bacteriological measurements of water in accordance with normalised procedure NFT904146 were carried out on the permeates taken from membrane pressure vessels or on permeates from skids. These bacteriological measurements can only be interpreted statistically because both positive and negative results could be biased (contamination or samples being to small to allow detection of coliforms). To allow analysis of the given data every box reading underwent an arbitrary notation resulting in the following. Presence of Positive Coliform Colony: Note 10 = 1 colony Note 20 = 2 colonies Note 30 = 3 colonies.. . .

4 OTV Laquarkne,
Maurice Cedex, France

1 Place Montgolfier.

94417

Saint

6 Detection tolerant filtration.

and enumeration -

of coliforms method

and thermoby membrane

colitbrms

General

5 DOW Filmtec, Minneapolis

C. Ventresque et al. /Desalination 131 (2000) l-16

Absence of Positive Coliform Colony and absence of interfering non-pathogenic flora (saprophytes): Note 0 Absence of Positive coliform colony but presence of interfering non-pathogenic flora (saprophytes): Note Note Note Note Note 1= 2= 3= 4= 5= O-10 saprophytes 1 I-50 saprophytes 5 l-100 saprophytes more than 100 saprophytes agar covered.

The notes were added when results consisted of both coli and saprophytes; for example, a note of 23 corresponds to 2 coliform colonies as well as 53 saprophyte counts on the same box.

3.2. On-line particle counting The on-line particle counter used to count particles at the inlet of the membranes makes use of two measuring canals (particle size superior to 0.5 pm and superior to 1.5 pm). Optic sensors analyse the diffusion (at 90) and the absorption (at 180) of light induced by the passage of particles in a laser beam (50 mW diode laser).

Literature [6] on the subject decrees that pretreatment be as thorough as possible in order to ensure, for example, an MFI [7] under 1 s/P and a DOC inferior to 1 mg/l [S]. Numerous pretreatments by ultrafiltration are reported. At M&y-sur-Oise, pre-treatment was defined by trial runs with an objective of insuring a SD1 of the order of 3, a particle content (size superior to 1.5 pm) of the order of 100 particles per ml, and a bacteriological content as low as possible. Several industrial pre-treatments were tested and evaluated economically. It is obvious that for the future, the choice of the pre-treatment must be kept within the responsibility of the designer of the entire operation because a thorough knowledge of the water resources specificity is required. Membrane manufacturers, for their part, must focus their efforts on developing membrane elements less subject to fouling and less expensive in order to reduce the total costs of those technologies. The pre-treatment performances for the period September 1999 to May 2000 as put into place in the plant are summarised in Table 1 below.

4.1. I. Colloidal fouling The pre-treatment in use permits the achievement of very low particle counts because particles over 1.5 urn are close to the limit of detection on leaving the pre-filters (cl 0 particles per ml). The tiny particles, counted from 0.5 urn onwards vary between 5,000 and 12,000 particles per ml which is low. (See Kruithof [9] who reports findings of 10,000 particles after ultrafiltration.). In Mery case, a high content of particles superior to 0.5 urn was regularly recorded (peaks) as shown by Fig. 2, these peaks appeared when the pre-filters were put back into service after backwashings. The automation of pre-filters has been reviewed to eliminate these peaks.

4. Discussion 4.1. Pre-treatment and cartridge pre-Jilters Pre-treatment is necessary to limit the blocking of membranes by colloidal particles (colloidal fouling) organic (organic fouling) or biological (biofouling). The quality conditions to attain are not clear. Suppliers of spiral membranes require that the SDI is inferior to 5 but rarely give limits for TOC or bacteria counts. 7 HIAC Royce 2000
Standard test method for silt density index. ASTM designation D-4189-82.

C. Ventresque et al. /Desalination 131 (2000) l-16

Table 1 Averages for the values taken for the period October 1999-May 2000 Parameter Particles related parameters SS, mg/L Turbidity, NTU Particle count > 1.5 pm/ml Particle count >0.5 pm/ml MFI (3 1Jan-l 5 March), s/l2 SD1 Bacteriological pararmeters SSRC, c/100 ml Total coliforms, ci100 ml Organics DOC, mg/l UV absorption River Oise Outlet storage Outlet Actiflo After dual layer After pretiltration filters

34.6 NM NM NM NM NM 172 10,084 4.65 107

18.9 20.9 NM NM NM NM 124 5,083 4.18 105

2.26 1.1 Around 4,000 NM NM NM 12.4 684 NM NM

NM co.05 22 NM NM NM All negative 0.4 2.1 NM

NM NM 2.3 7,258 a 3.35 h, 2.8 All negative 0.4 2.1 35.6

a) Particle counts above 0.5um varied between 5,000 and 12,000 per mL; b) The MFI varied between 0.2 and 8 s/P; c) Spores of sulfite reducing clostridia; NM - No measurement.

a,

Backwashings of prefilters

07/04/00

08/04/00

09/04/00

10/04/00

Date as day/month/year Fig. 2. Particle counts above 0.5 urn as thousand per ml at the outlet of the prefiltration unit as related to occurrence of backwashings of pre-filters.

C. Ventresgue et al. /Desalination 131 (2000) l-16

25 XMFI -left axis

0
20 ~__ _*-----_---------

OTurbidity

of water at outlet of rtver storage - right axis

0
15

0 OO

__0 OO

co

------zj=+0 0

g 10 ii z

maw=@
00
0
24/02/00 05103/00 15/03/00 25/03/00

15/01/00

25iO1100

04/02100

14/02/00 Date

as day/month/year

Fig. 3. MFI (mean daily value) at the outlet of the prefiltration unit and turbidity of the water at the outlet of the river storage (NTU mean daily value).

100000

Fig. 4. Effect of pretreatment on total coliforms counts.

C. Ventresque et al. Llesalination

131 (2000) I- I6

3 i
YI

E!

2: 9

.---_-!&-__16104100 16105100

Date as day /month

I year

Fig. 5. Water productivity for the 4 skids of unit #6. Skid #I and skid #2 are first stage skids operated in parallel. Skid #3 is second stage, skid #4 is third stage. UP = cleaning in place (all products as liquid); SH = sodium hydroxide; CD = caustic detergent (Ultrasil 110 by Henkel); CA = citric acid; PAA = peracetic acid.

A campaign of verification of the MFI took place between the 30th January and the 15th March 2000. The MFI leaving the pre-filters is variable between 0.2 and 8 s/l2 with an average around 3 s/P. As for particles superior to 0.5 pm the MFT is higher at the putting back into service of the pre-filters after backwashings. On the long run, the MFI seems to be sensitive to the flooding of the Oise (Fig. 3).

4. I. 3. Organic fouling The quantity of organic matters at the entrance to nanofiltration is around 2 mgC/l (as DOC) which is acceptable. The UV absorption is well eliminated by the pre-treatment.

4.1.4. Results upon the permeability membranes

qf the

4.1.2. Biofouling The pre-treatment put into operation permits to reach more than 4 log of reduction for the total coliforms (Fig. 4), after the dual layers filters the efficacy is no longer measurable. The other parameters are also well eliminated.

Upon putting the membrane lines into service the permeability of the membranes was 7 1 h-me2 bar-. During the first few weeks of operation the permeability levels descended to around 6 1 h-rn- bar-. It then stabilised at this value for the 1.0 to 15 months, which elapsed after the progressive putting into service of the 8 membrane units. Automatic cleansings were effectuated about every two months except for

C. Venfresque ef al. /Desalination 131 (2000) 1-16

the earlier period during which they were more frequent. Fig. 5 shows the case of the unit N 6.

4.2. Control-checking the purchase of the mem-

brane elements
The 9,120 membrane elements were subjected to a specific control-check during manufacture. This control check was concentrated upon the flow produced by membrane element, the head loss in the concentrate side of the element as well as upon the passage of calcium, the retention of atrazine, along with sulphate of magnesium. These tests allow the covering of the performances desired for Merysur-Oise. They are described in Table 2. They can be realised upon different sites on test skids. About 10% of the elements manufactured were tested under standard conditions (under approximately 5 bars) with two types of synthetic water at a temperature of 25C. The choice of elements was done at random. Two standard tests were done on each element - a test with demineralised water to which had been added
Table 2 Tests for NF200-B-400 held for M&y-sur-Oise Test for manufacturing faults in the elements. Hydraulic tests

500 mg/L of CaC12 and 4 ug/L atrazine and a test with demineralised water to which had been added 2 g/L of MgS04. The flow for each membrane and the concentrate head loss were measured during the test for CaC12. The results obtained out of more than 1,000 modules, Figs. 6 and 7, showed that the passage of magnesium sulphate was less than 3%, the mean value for retention of atrazine was 97.2%. The passage of calcium and the water permeability are more variable around the average value but the average value is well above the minimal performances which had been demanded. The results of the tests serve as a way of checking, as well as also giving a set of references which allows us to follow up on the evolution of the elements performances during time, once they have been put in place within the water treatment plant. The elements which were tested were put in labelled pressure vessels and spread among the different blocks of the 8 membrane units. If there is need, they can be taken out of the pressure vessels and tested under the conditions of a standard test.

The passage of magnesium sulphafe is an indication of the integrity of the element (the absence of faults whether in the membrane itself or in the glue joints), the retention of magnesium sulphate must be the highest possible. ThefIow produced by the element gives a value of the permeability to water which must be the highest possible. An average value of 29 m3/d was required. The concentrate head loss must be the lowest possible, which indicates a homogenous rolling of the membrane leaves permitting them to function with the least energy possible.

Performance tests linked to the quality of water.

Atrazine was chosen as surrogate for organics, it being often present in the waters of the Oise. As well as that, it has a rather low molecular mass (200 Dalton), it therefore allows of the testing of organic matter retention the size of which is superior to this value. The retention of organic matter actually seems roughly linked to the molecular size of the organic compound [lo]. For M&y-sur-Oise, it was asked that mean atrazine retention be equal to a minimum of 95% under the conditions of a standard test. The passage of calcium to the contrary should be high enough so that it wouldnt be necessary to process a remineralisation of water leaving the membranes. The passage of calcium is influenced by temperature. An average value of 55% was demanded.

IO

C. Ventresyue et al. /Desalination 131 (2000) I-16

100%

I,<._,

90% ,

.,
-.-..--.-./--,

80%.

70% ,~

~,

60%

m-: . Magnewm Suiphafe

Fig. 6. Magnesium sulphate and atrazine passage cumulated histograms (passage expressed as concentration of product in permeate/concentration of product in feed water as %) for all membrane elements tested.

,009,

.,, ..,.._ ...~ .._.-l .,..,.....,.,. ^._ ....

-Flow per module as m3 per

E.
rf si i

day

~_-__._.i._ __ .,
. i *I ,

sax .&)% .._ 70%

. . . . . Cakiun

passage as 55

.~ .,..,._. .._ _ .-.- .-.-.-~

,.. .._._ . .. _-..X. . ._..-____I I : ._.

._ --._z_.

6096 . %
40% 1

I
I ^ _.^. .._ .- _-._. . .--. . ..._.

30% .20%

..

._...... _._

,
2
. . ..-

_..__ .._

10%

0%

..

Fig. 7. Cumulated histograms for water production (as m3/d) and calcium passage (calcium in per-meatekalcium water as %).

in feed

C. Ventresque et al. /Desalination 131 (2000) I-16

11

4.3. Membrane system integrity

As far as the elimination of pathogenic micro-organisms is concerned, nanofiltration and reversed osmosis processes still have not obtained the recognition they deserve from sanitary authorities, whether they be in Europe or in the United States. This is due to the lack of data and studies upon the real capacity of systems expressed in Log removal - to eliminate pathogens [I l] and to the lack of system for checking leaks and defects. M&y sur Oise being a Frances first, the sanitary authorities demanded that a disinfecting process being placed after membrane filtration as a precaution. Due to the high purity of the water, UV irradiation has been chosen and accepted. It has been demonstrated [ 121 that for disinfection purposes, integrity measurements and monitoring of membrane systems are essential. The expected log removal is altered when the nanofiltration modules are not fitted properly in the system. For M&y, in spite of an UV disinfection after nanofiltration it has been decided to perform integrity measurements of membranes. This was done both at the manufacturers site on the elements and on the system during themselves commissioning.

and pressure. This test is able to point out leaks through the glue lines in the membrane elements or leaks in brine seals as well as holes in the membrane itself. 4.3.2. Additional module integrity tests M&y-sur-Oise being the first application of NF200 nanofiltration membrane to such a scale, the SEDIF decided to implement a thorough survey of the 9,120 modules. The survey consisted in selecting approximately 10% of the membrane elements before they left the manufacturers plant. The selection was done by the SEDIF, at random, on the finished batches. The random drawn elements were submitted to a magnesium sulphate test.

4.3.3. System integrity tests The integrity test which was implemented on the system consisted of sampling water on the smaller production unit of the system. For RO and nanotiltration the smaller production unit is a skid or better still, a pressure vessel. In MCrysur-Oise, there are 1,520 pressure vessels arranged in 32 skids. The higher risks of leaks are located at the seals between modules and between modules and caps in a pressure vessel (internal leaks). There are 22,800 seals in the system in Merysur-Oise. A common practice for detecting leaks consists in sampling conductivity for each pressure vessel. Unfortunately, for nanofiltration, due to the relatively high passage of salts, the conductivity is not adequate as it is shown in Fig. 8. This figure gives the repartition of conductivity measured at the outlet of the 54 pressure vessels of a second stage skid. A single tube, #22, showed high conductivity but was not leaking, on the contrary two tubes, # 45 and # 81 was leaking but their conductivity was OK.

4.3.1.

Module integriv

tests by manufac-

turer
Each element is submitted to a vacuum test for detecting leaks between the feed and the permeate. The test adapted by DOW-FILMTEC for NF200B-400 elements is derived from the ASTM D3923-80 method. Each element produced is vacuum tested. When an element fails the vacuum test it is tested for sulphate retention. The sulphate retention test consists of operating the element with water spiked with 2 g/L of magnesium sulphate. The test is performed on the element under controlled temperature, pH

12

C. Ventresgue et al. /Desalination 131 (2000) l-16

350

IP 3 v D f a, 250 ; i H 'i; 200 g! I E B :: g s -z s 50 100 150

I

4!rv *. .. .. . . ..

--1
.. ..

300

..

..

_~

._ _ .

..

__ .rn%. . .. .. I I -lr -I
I

81

conductlvlty

produced

.. ..

e--

by the skid

I I

Fig. 8. Conductivity measured in the permeate of 54 pressure vessels for one second stage skid.

Fig. 9. Sulphate measured in the permeate of 54 pressure vessels for one second stage skid (same skid as in Fig. 8)

C. Ventresque et al. /Desalination 131 (2000) 1-16

60 pressure vessels showing sulphate in permeate

13

70

meate

; f I e ; g % & z r e t

60

50

40

30

20

10

0 Less than 2 2 to 5 Notation as described 5to10 In material 1oto50 and methods MOW than 50 Number of Pressure vessels sampled : 135

Fig. 10. Coliform countings on pressure vessels before and after sulphate correction campaign.
60

.._...... ___..iII .__. .._.

-.

..__..... .._.

..^^

50

40 * P Y In ;I z? J : 0 . : 20 30 Colt counted

IO

7
Less than 1 1 to 5 Notation as described 5to10 in Mater~el and

N urn ber

of skids

sampled

: 11 1

0
10 Methods to 50 More than

Fig. 11. Influence of one compromised pressure vessel (showing sulphate in permeate) on the bacteriology measured for the skid (28 pressure vessels for Skids #4, 54 pressure vessels for skids #I to 3).

14

C. Ventresque et al. /Desalination 131 (2000) l--l6

Probing the conductivity by inserting a probe through the permeate channel of each pressure vessel and collecting and analysing samples at different locations is a second possibility [ 131. But, it would have been time consuming (1,520 pressure vessels) and impossible to implement in M&y-sur-Oise due to the difficulty in installing the probes (shutting down the system, installing numerous probes, putting the system back into operation). Furthermore, conductivity profiles are often difficult to interpret and small leaks are not always visible. Taking into account the impossibility of probing all the 1,520 tubes and faced with the deficiency of the conductivity measures at outlet of the pressure vessels to detect leaks, the trials were done with sulphate measures. It was processed during the operation set-up to the measurement of sulphate within the permeate produced by the 1,520 pressure vessels. This process allows the detection of leaks through either a membrane element or within the system, without there being any stoppages of running. This detection could be done pseudo-continuously in some minutes. The sulphate ion presents numerous advantages for detecting leaks between the concentrate and the permeate: Being an ion of strong acid, it stays unchanged whatever the pH of water, its passage through the membranes is constant despite the variation of pH between the alimentation of the membranes and the final concentrate. Its dosage is rapid and cheap. It can be done on site with a kit and a field spectrophotometer. It is present naturally superficial waters. in seawater and

the pH entering the membranes which increases yet again the quantity of sulphate in the concentrate side of the membranes, thus allowing the detection of very slight leaks. The measurements of sulphate performed at the outlet of the 54 pressure vessels of one block for which the conductivity is presented in Fig. 8 has given the results presented in Fig. 9. Two pressure vessels, #81 and #45 showed a strong presence of sulphate. During the setting-up of the plant, while a strong presence of sulphate was detected exiting a pressure vessel, which was the case for 99 out of 1,520 pressure vessels, a profile along the length of the permeate tube within the pressure vessel was done which represented just about 6.5% of the pressure vessels. In practice the systematic measuring of sulphate in the permeate of 1,520 tubes and probes along the length of the pressure tubes allowed the correcting of defaults, essentially: 1. The replacement connecting joints. of flat or rolled inter-

2. The fixing of missing joints. 3. The fixing of missing connectors. 4. The changing elements. of four broken membrane

Even more in large units, sulphuric acid is often preferred to chlorhydric acid for adjusting

During this campaign of correcting leaks, the bacteriological samples taken from the waters were performed on the permeates of the pressure vessels before and after correction (about 140 germ counts). The results are shown in Fig. IO. It appears that the tubes which leak sulphate could also present germ leaks. On the other hand, those tubes in which the sulphate was at satisfactory levels, showed no germ leaks. As regards to the blocks which are constituted of 28 or 54 tubes the result of one or several pressure vessels of which the integrity is not absolute is given in Fig. I 1.

C. Ventresque et al. /Desalination 131 (2000) l-16

15

5. Effkiency of membrane

NF200B-400

Since commissioning, the efficiency of TOC retention for the new facility of M&-y-sur-Oise is at an average of 95.5% with an average value of 0.18 mg/l of TOC in the permeate produced. In the period September 1999 to May 2000, no pesticide neither by-product of pesticide has been detected at the outlet of the plant over 128 analyses (detection limit is 50 nanog/l). During this period Oise River has not being subject to heavy pollution as regards pesticides, the maximum value recorded at inlet of the facility has been 440 nanog/l for atrazine and 220 nanog/L for diuron. As far as the retention of calcium and bicarbonates are concerned, filtration on membranes NF200B-400 allows the production of less impoverished water. Nanotiltration preserves bicarbonates to a degree of 30-60% in relation to the temperature (Fig. 12) which avoids the need of a recarbonisation of the water. Calcium and magnesium are preserved to a degree of 20-55% in relation to the temperature.

Temperature of the Feed water (C)

Fig. 12. Bicarbonate in permeate expressed as percentage of bicarbonate at the inlet of the nanofiltration.

(excluding VAT) per cubic. This extra cost will be compensated for by savings in other areas. The M&y-sur-Oise plant extension has therefore not lead to a price increase for customers.

References
K. Agbekodo, 8. Legube and P. C&C, J. AWWA, May (1996) 67. PI A. Boireau, G. Randon and J. Cavard, J. Water SRT Aqua, 46 (4) (1997) 210. i-31 C. Ventresque and G. Bablon, The nanofiltration integrated system of M&y-sur-Oise Surface Treatment Plant (37 mgd), Workshop on Membranes in Drinking Water Production. Technical Innovations and Health Aspects, IWSA, LAquila, Italy, June l-4, 1997. F. de Dianous, E.Pujol and J.C. Druoton, Proc., 4th [41 Gothenburg Symposium, Madrid, Spain, l-3 October 1990,lO (1990) 127. C. Ventresque, G. Turner and G. Bablon, J. AWWA, [51 October (1997) 65. II61 S. Chellam, C.A. Serra and M.R. Wiesner, J. AWWA, November (1998) 96. J.C. Schippers and J. Verdouw, Desalination, 32 171 (1980) 137. J.P. van der Hock, P.A.C. BonnC, E.A.M. van Soest PI and A. Graveland, Water Supply, 16 (l/2) (1998) 313. PI

6. Conclusions The M&y-sur-Oise membrane facility has produced 140,000 m of permeate per day since September 1999. This new facility allows, starting from the highly degraded and variable waters of the Oise, to produce water that is exceptionally pure. The quantity of organic matter is very low and the biodegradable part of its organic matters below the limits of detection of the measuring. The operation of the new facility is ensured by the conventional personnel assisted by a maximum degree of automation. The cost of the entire operation, including the new plant and various adaptations to the conventional plant, is around 130 million Euro excluding VAT. The additional cost of treating water by nanotiltration is estimated at 0.12 Euro

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J.C. Kruithof, J.C. Schippers, P.C. Kamp, H.C. Folmer and J.A.M.H. Hofman,. Proc., AWWA Annual Conf., D (1998) 387. [IO] B. van der Bruggen, J. Schaep, W. Maes, D. Wilms and C. Vandecasteele, Desalination, 117(1998) 139. [ 1l] Manual of water supply practices. Reverse Osmosis and Nanofiltration, AWWA Manual M46, First

Edition, 1999. [12] M.M. Nederlof, J.C. Kruithof, J.A.M.H. Hofinan, M. de KBning, J.P. van der Hoek and P.A.C. Bonn&, Desalination, 119(1998) 263. [13] S. Adham, P. Gagliardo, D. Smith, D. Ross, K. Cramith and R. Trussel, Desalination, 119 (1998) 143.