DESALINATION

ELSEVIER Desalination 170 (2004) 41-47

www.elsevier.com/locate/desal

Study of drinking water treatment by ultrafiltration of surface

water and its application to China
Shengji Xia*, Jun Nan, Ruiping Liu, Guibai Li
School of Municipal and Environmental Engineering, Harbin Institute of Technology,
PO 279, Huanghe Road HIT, 150090 Harbin, China
TeL +86 (451) 8684-2032; Fax +86 (451) 8230-6643; email: xiasj@sina.eom

Received 16 September 2003; accepted 15 March 2004

Abstract
In China, many water supplies depend on conventional water treatment. Due to unfit soil and water conservation
in some regions of China, conventional water treatment has showed some defects for the poor quality of water resource.
In addition, advances in membrane technology and increasing requirements on water quality have stimulated
ultrafiltration (UF) for water treatment. In this research, UF test apparatus was set up to produce drinking water from
raw water of the Binxian Reservoir (China). The performance of UF membranes was investigated. There was a linear
relationship between membrane resistance and accumulated permeate water. Using coagulation before UF increased
permeate flux and retarded membrane flux decline. Surprisingly, membrane permeate flux in a coagulation/UF process
was higher than that in coagulation-sand filtration-UF process with raw water of medium turbidity. UF treatment
provided effective turbidity removal. Iron, manganese and aluminum were removed completely. The UF membrane
also perfectly removed all coliform bacteria. The reduction of total organic carbon was satisfactory. The treated water
quality complied with China's drinking water guidelines. The Ames test showed that the mutagenic activities of
membrane permeate water was negative.

Keywords: Ultrafiltration; Drinking water treatment; Pretreatment; Surface water; Ames test

1. Introduction
In China, many public water supplies depend
on conventional water treatment. A conventional
surface water treatment plant may include a
multi-step process applying chemical addition,
*Corresponding author.
coagulation, flocculation, sedimentation, filtration
and disinfection, usually with chlorine. Each step
o f this process has to be controlled to get optimal
performance o f the overall process, which results
in a complex system. In recent years, membranes
such as microfiltration (MF) and ultrafiltration
(UF) in drinking water treatment have become a

0011-9164/04/$- See front matter © 2004 Elsevier B.V. All rights reserved

doi: 10.1016/j.desal.2004.03.014
42 S. Xia et al. / Desalination 170 (2004) 41-47

more attractive technology as a possible alter- 2. Experimental

native to conventional clarification. UF tech-
2.1. M e m b r a n e s
nology has many advantages in comparison with
conventional process such as clarification and UF membranes made o f PAN were used in the
disinfecting. The main advantages are [1-3]: experiments. The nominal molecular weight cut-
• compact process and plant off of these membranes as reported by the manu-
• separation takes place by size exclusion facturer is 50,000 Dalton. Characteristics of the
• invariable quality of produced water membranes are shown in Table 1.
• constant production and water quality inde-
pendent of feed water quality Table 1
• easy automation Membrane characteristics data
In this paper we report the results o f UF
Parameter UF membranes
experiments with polyacrylonitrile (PAN) mem-
branes fed with raw water drawn from the Type Hollow fiber
Binxian Reservoir located near Harbin in China. Material PAN
The purpose o f this study was to evaluate the UF Molecular weight cut off, Da 50,000
performance in terms of flux and quality of Length, mm 248
treated water. The second purpose was to Hollow fiber internal diameter, mm 0.9
Hollow fiber external diameter, mm 1.5
examine the feasibility of the UF process to
Membrane surface area, mE 0.56
produce drinking water in China from raw water
pH-range of operation 4-9
of poor quality due to unfit soil and water Temperature-range, °C 5-45
conservation.

. . . . .

I
I
I
Y
J I
I
I
I

I
I
I
I I
PACI
V
I +
raw
-,1 1 I I
I

I I ),
water I I
setting tank I discharge
t discharge ate tank
~ eletromagneticvalve adjustable valve - in-line filter
A sand filter pump t)-? globe valve
B UF module @ pressure meter flow meter Fig. 1. Schematic flow diagram of
C turbiditymeter the experiment.
 S. Xia et aL / Desalination 170 (2004) 41-47
2.2. Ultrafiltration test apparatus and procedure
Fig. 1 shows a schematic diagram of the UF
experimental facility. The system consists of two
parts: a crossflow UF unit with a recirculation
and permeate backwashing. The reservoir water
was taken from a supply pipe to a settling tank.
If the turbidity of raw water was low, it was
pumped to the UF membranes for direct UF. As
to high turbidity of feed water, pretreatment by
sand filtration was in operation, flocculation
agents being dosed when necessary. In the UF
phase, the water was filtrated from inside to
outside of the hollow fiber. Backwash of the UF
mode (duration of 45 s) was made during a 30- to
80-min interval. In the backwash phase, the
washing water was sent to be pressurized from
the outside about 0.2 MPa to the inside of the
hollow fiber. Pressure gauges and electromag-
netic flow meters were used to control the
operating performance.
2.3. Salmonella/microsome assay (Ames test)
To assess mutagenic activity of treated water,
Ames tests were performed. Water samples were
drawn with raw water and permeate water in a
coagulation-sand filtration-UF process. The
Ames test was carried out as the standard plate
incorporation test [4] with Salmonella typhi-
murium strains TA98 and TA100. In this work it
was done without in vitro microsomal activation
($9 mix) because most of the natural mutagens
are direct acting and do not require activation [5].
Concentration of water samples was performed
according to the procedure recommended by the
US EPA (Life Systems, 1985) with XAD resins
(XAD-2 and XAD-7 columns) with a concen-
tration factor of 1:10000. Concentrated water
samples were tested in triplicate with four doses:
100, 300, 500 and 700 #1. Mutagenic activities
were expressed by induction factors, as multiples
of the background levels. The results were con-
sidered positive if the highest non-toxic dose
43
level produced a response that was twice as high
as that found with the solvent control. Positive
controls giving a significant increased number of
revertants compared to the negative controls were
(Dexon) for TA98 (60 #g/plate: revertants/plate
1462+8) and TA 100 (60 #g/plate: revertants/plate
13564-259); negative controls with dimethyl sulf-
oxide (DMSO) were 50 4- 7 revertants/plate for
TA98 and 140 4- 15 revertants/plate for TAt00.
3. Results and discussion
3.1. Membrane resistance
Transmembrance pressure (AP) was calculated
according to the following equation:
AP = (Pfo~d+ Pconc)/2- Pperm
where Pfoodis the feed pressure (MPa), Pconc the
concentrate pressure (MPa) and Ppermthe perm-
eate pressure (MPa). Membranes resistance was
calculated using the following equation:
Ap
R-
#xJ
where R is the membrane resistance (m-1), AP the
transmembrance pressure (MPa), I.t the water vis-
cosity (Pa.s), and J is the flux (Lm-Zh- 1).
In the procession of UF, feed water was divi-
ded to permeate flux and concentrate. Fig. 2
shows the flux and membrane resistance in-
creased during crossflow UF at a constant trans-
membrane pressure of 0.1 MPa. There is a linear
relationship between membrane resistance and
accumulated permeate water, and this can be
described by the equation: Y= 0.008X+ 1.2488.
3.2. Membrane flux decline
The effect of raw water turbidity on UF
behavior for the PAN membrane is shown in
Fig. 3 where the measured flux is plotted against
44 S. Xia et al. / Desalination 170 (2004) 41-47

2.4 ¸ 250 .
y = 0.008x + 1.2488 -..+...Raw water: 20NTU
~ 2,2 ¸
200 4? .......Raw water: 110NTU
~ 2.0 ¸ ]'(.~.. ~ R a w water 450NTU

1.8

9 J.6
'~ 1.4.

1.2. 50 ¸

1.( I I I I I
20 40 60 80 100 120 I I I I I
I0 20 30 40 50 60
Accumulated permeate volume(L) Run time (minutes)

Fig. 2. Increase in membrane resistance for ultrafiltration Fig. 3. Direct ultraflltration of raw water with different
of raw water. turbidity.

250 220

200 210
j~,ff
200 /
,..~ 150 //
190
IO0 I } I I I

0 10 20 30 40 50 60 180 I I I I
D a y s o f operation 0 I 2 3 4 5
Dosage of coagulant added (rag/I)
Fig. 4. Permeate flux for a long time and its recovery by
chemical cleaning. Fig. 5. Effect of coagulation on ultraflltration flux.

time with raw water. We can see from the figure:
the rates of permeate flux decline were different
according to feed water quality. With the feed
water of 20 NTU, membrane flux decreased to
about 50% of initial flux after 60 min; contrast to
450 NTU, only 10 min passed where the mem-
brane flux decreased to 50%.
Although backwash with permeate water can
recover membrane flux, for a long time the flux
will decrease, and a chemical cleaning may be
required to restore the initial performance of the
membranes. Fig. 4 shows the permeate flux over
60 days during the test periods. As shown in
Fig. 4, chemical cleaning (Nov 5, 2002) with
citric acid solution alone increased the permeate
flux to initial level effectively.
3.3. Coagulation-ultrafiltration
Pomtip et al. introduced the coagulation step
before UF as an excellent pre-treatment method
for particle removal [6]. The coagulation-UF
process can be used to treat poor-quality surface
water: permeate quality is increased and mem-
brane fouling is reduced [7]. Fig. 5 shows
membrane flux vs. dosage of coagulant added
before UF. As can been seen, for the raw water
(turbidity = 23.0 NTU), direct UF could get a
permeate flux of 190 L/m2h, with a transmem-
brane pressure 0.1 MPa. When dosing coagulant
(PAC1 1 mg/1 and 2 mg/1) to this water, permea-
bility had little change in comparison with that of
no coagulants added. But the permeate flux
increased when the coagulant added to 3 mg/l. At
 S. Xia et aL / Desalination 170 (2004) 41-47
230
210
~ , 190
~,.~ 170
150
130
110
0 1
Dosage o f coagulant added (rag/l)
Fig. 6. Effect of sand filtration on ultrafiltration flux.
the same time, we observed that the floc was
large and the characteristics of its settling were
good. As can being seen from Fig. 6, the optimal
concentration may be determined as C = 3 mg/1.
This increase in the permeate was due to floe
formation, whose dimension did not permit the
fouling of pores. Fig. 6 compares membrane flux
of coagulation-UF to that of the coagulation-
sand filtration-UF process. There is a surprising
finding: for Binxian Reservoir water (25°C) with
turbidity of 25 NTU, the permeate flux ofcoagu-
lation/UF was higher than that of coagulation-
sand filtration-UF in five out of six experiments
for different dosages of coagulant added. This
unexpected observation may be explained by the
assumption that the principle of UF is by means
of size exclusion. If the target size is larger than
the UF membrane pore, it is rejected by the
membrane. Otherwise, it passes though the UF
membrane. When raw water is coagulated with
coagulants, we assume the possibility of the
different size offlocs existing is identical. In the
coagulation-sand filtration-UF process, the frac-
tion of large-sized floc was rejected by sand
45
2 3 4
filtration, and what remained was small-sized
colloidal matter, which has the same dimension as
the UF membrane pores. The small-sized colloids
are embedded in the pores so UF membranes
were prone to fouling under this circumstance. As
to the coagulation-UF process, large-sized parti-
cles whose dimension were larger than the
membrane pores form an easily removable and
permeable layer on the membrane where colloids,
algae and other suspended mater will be trapped
or adsorbed by the layer so that they cannot
physically block the membrane pores.
3.4. Permeate quality
Table 2 lists chosen water parameters
measuring raw water, direct UF permeate water
and coagulation-UF permeate water. The Binxian
Reservoir is characterized by a turbidity ranging
from 3.5 to 500 NTU with high variations due to
run-off events.
Retention of the trace metals A1, Fe and Mn
was detected. This was caused by adsorption
effects on the membranes which resulted in
46 S. Xia et al. / Desalination 170 (2004) 41-47

2.5
Table 2
The quality of raw water and UF permeate water determine standard S
2.0
Parameter Raw Direct Coagulation/
water UF UF -= 1.5

Turbidity, NTU 23 0.1 0.1 1.0 I 1 I I t I I

COD, mg/1 5.3 4.4 3.7 1 2 3 4 5 6 7
Dosage of concentrated water (ul/plate)
TOC, mg/1 5.7 4.3 3.3
Conductivity, ~s 254 248 265 Fig. 7. Genotoxic activities expressed as induction factors
NO3, mg/1 1.01 1.01 0.90 (TA98).
A1, mg/1 0.69 <0.002 0.029
2.5
K mg/1 3.894 3.633 3.635
determine standard
NH~, mg/l 0.04 0.02 0.02 2.0
o
Fe, mg/1 0.415 <0.002 <0.002 eoagulation/UF
1.5
Mn, mg/1 0.019 0.002 0.003
o
Ca, mg/1 30.69 29.45 35.76 '~ 1.0
Total coliform, c/ml 160 0 0
~ 0.5

fouling and thus in a decrease in permeability. UF
treatment provides effective turbidity removal
with an average o f 0.1 NTU. The reduction of
TOC was satisfactory. The permeate TOC and
COD values were 4.3, 4.4 and 3.3, 3.7, respect-
ively. The UF membrane also appears as a disin-
fection step by completely removing coliform.
3.5. A m e s test
The Ames test reveals the gene mutation
inducing ability. Out o f the Ames test preformed,
a weak but significant mutagenic activity with
strain TA98 was obtained. Figs. 7 and 8 show the
inducing factors of different concentration of
water samples. The raw water sample (700 #1
extract per plate equivalent to 7 L of native
sample) yielded an induction o f 2.2.
4. Conclusions
UF of surface water with PAN membranes
was proven very useful for drinking water
production.
0.0 f I t I I
1 2 3 4 5 6
dosage of concentratedwater (ul/plate)
Fig. 8. Genotoxic activities expressed as induction factors
(TA100).
The reduction in turbidity of the UF mem-
brane was very efficient throughout the investi-
gation with permeate turbidity o f 0.1 NTU. Iron,
manganese and alum were removed completely,
except in the coagulation-UF process using PAC1
as the coagulant. The UF membrane also per-
fectly removed all coliform bacteria. The reduc-
tion o f TOC was satisfactory. With the exception
o f one weak positive effect o f raw water samples,
the Ames test showed that the mutagenic acti-
vities in membrane permeate water were
negative.
In China, for surface water o f high turbidity
and fairly variable quality, a coagulation step
prior to UF should be considered. The addition of
coagulant not only increases the permeate flux
but also retards the permeability decline. A new
phenomenon was observed in our experiment:
membrane flux in the coagulation-UF process
 S. Xia et al. / Desalination 170 (2004) 41-47
was higher than that in the coagulation-sand
filtration-UF process with raw water o f high
turbidity.
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[4] D.M. Maron and B.N. Ames, Revised methods for
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