Separation and Purication Technology 65 (2009) 193210

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Separation and Purication Technology

journal homepage: www.elsevier.com/locate/seppur

Application of coagulationultraltration hybrid process for drinking water

treatment: Optimization of operating conditions using experimental design
A.W. Zularisam a,b,c , A.F. Ismail a, , M.R. Salim c , Mimi Sakinah a , T. Matsuura d
a
Advanced Membrane Technology Research Center, Universiti Teknologi Malaysia, 81300 Skudai, Johor, Malaysia
b
Faculty of Civil & Earth Resources, Universiti Malaysia Pahang, UMP, 25000 Gambang, Pahang, Malaysia
c
Faculty of Civil Engineering, Universiti Teknologi Malaysia, 81300 Skudai, Johor, Malaysia
d
Industrial Membrane Research Institute, Department of Chemical Engineering, University of Ottawa, 161 Louis Pasteur Street, P.O. Box 450,
Station A, Ottawa K1N 6N5, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Coagulation application prior to ultraltration process was carried out to increase NOM removal and
Received 21 July 2007 membrane permeability. A systematic experimental design based on rst order model of 24 full factorial
Received in revised form design was used as an initial screening process to determine the signicant variable factors and their
15 September 2008
inter-relationship towards natural organic matter (NOM) removal efciency. The factors considered were
Accepted 4 October 2008
SUVA (specic UV254 nm absorbance), FRT (occulation retention time), alum dosage and pH. Statistical
analysis of result has shown the main effect of alum, pH, SUVA and the two level interactions of alum and
Keywords:
FRT, alum and SUVA, alum and pH, FRT and SUVA, and SUVA and pH were the signicant model terms.
NOM
Flocculation
Thereafter a second order model which was the 23 central composite designs (CCD) was further employed
Coagulation to develop a mathematical correlation model between the signicant factors for the optimum modes of
Membrane operating condition, with respect to NOM removal and membrane permeability. The alum dosage is found
Drinking water to be the most signicant factor that inuences the NOM removal and this is followed by the two level
interactions of pH and SUVA, the main effect of pH, the main effect of SUVA, the two level interaction
of SUVA and alum, the second order effect of SUVA and the second order effect of pH. In the case of
membrane permeability, the main effect of alum dosage and the second order effect of pH provided the
principal effect, whereas the second order effect of alum, the main effect of pH, the two level interaction
of pH and SUVA, the two level interaction of SUVA and alum dose, and the main effect of SUVA provided
the secondary effect. The optimized values of 5.48, 3.24 L/(m mg) and 3.0 mg Al/L of pH, SUVA and alum
dose were obtained respectively, and with these proposed optimized conditions, a NOM removal of 81.28%
and permeability of 30.61 LMHBar was predicted. Thereafter via experimental validation process, 79.50%
and 31.29 LMHBar of NOM removal and permeability was attained, respectively. In conjuction treatment
efciency has shown excellent water quality that is well beyond the Malaysian and WHO drinking water
quality regulations with > 96% colour removal, about 87% UV254 removal, < 0.2 NTU, > 99% suspended solids
removal. and > 99% of turbidity removal.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Membrane ltration process involving microltration (MF),
ultraltration (UF), nanoltration (NF) and reverse osmosis (RO) in
potable water production have increased rapidly for the past decade
and would potentially replace the conventional treatment which
consist a complex series of unit operations, such as ozonation
precipitationcoagulationocculationchlorinationgravel ltra-
tion [1,2]. As part of drinking water treatment processes,
Corresponding author. Tel.: +60 7 5535592; fax: +60 7 5581463.
E-mail address: afauzi@utm.my (A.F. Ismail).
Ultraltration (UF) has been known to be effective for the removal
of suspended solids, colloidal material (>0.1 m), inorganic par-
ticulates and fatal microorganisms such as colliform, protozoa,
giardia and cryptosporidium [3,4]. In spite of offering high per-
meate ux and low pressure requirement, this ltration type is
relatively found to be less successful for wide application, par-
ticularly in removing the dissolved organic matters (DOC) such
as natural organic matter (NOM) which is regarded as a major
factor for membrane fouling and poor permeate quality [5,6]. In
fact removal of NOM which is inherently present in the form
of DOC or colloidal material is required, since NOM is a pre-
cursor to the formation of carcinogenic disinfection by-products
(DBP), aesthetically unattractive, carbon source for biolm growth

1383-5866/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2008.10.018
194 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210

in the distribution network and often reclaimed as an impor- Table 1

Characteristics of Yong Peng NOM source water.
tant factor for both reversible and irreversible membrane fouling
[7,8]. In the case of drinking water ltration the colloidal mate- UV254 nm (cm1 ) 0.174 (0.015)
rial may reduce the membrane permeability (reversible fouling) DOC (mg/L) 5.36 (1.27)
SUVA (L/(mg m)) 3.24
by accumulating solutes on the adjacent membrane surface (con-
Turbidity (NTU) 14.1 (5.1)
centration polarization), precipitating and forming a cake or gel Mn2+ (mg/L) 0.28
layer as they become supersaturated [9], while the DOC may Ca2+ (mg/L) 2.16
cause irreversible fouling by altering the effective membrane Al3+ (mg/L) 5.95
pores through precipitating and absorbing onto the membrane The numbers in parenthesis are standards deviation.
matrix and within the pores space. Hence coagulation pretreat-
ment prior to membrane ltration has been widely researched as
2. Materials and methods
a mean of removing non-settleable NOM content and reducing
membrane fouling through agglomeration of alum salts with the
2.1. NOM source water, isolation and concentration apparatus
destabilized particles before gravity precipitation [1013]. Previ-
ous studies using integrated conventional coagulation followed by
Selected Malaysian surface water source of Yong Peng water
direct membrane ltration or an inline coagulation (without set-
was used as a model solution for the membrane permeability and
tling) combined with direct membrane ltration [10,11,14], have
NOM rejection efciency of coagulation-direct UF experiments. The
demonstrated effective control of fouling, improved membrane
surface water quality and its NOM fractions characteristics are sum-
permeability and superior permeate quality despite having applied
marized in Table 1, Table 2 and Fig. 1, respectively. NOM of Yong
on low quality water sources. In details, coagulation pretreatment
Peng water was pretreated with 0.45 m lter paper (Whatman
of NOM with metal salt ions of Al3+ has been used to alter the
GC) prior to coagulation process while preparation of surrogated
NOM characteristics such as the relative content of NOM com-
SUVA was carried out by concentrating the NOM source using cel-
position (hydrophilic versus hydrophobic), NOM occulant size
lulose acetate reverse osmosis (RO) membrane. The concentration
and charge density possession, prior to UF membrane ltration.
module unit was designed and modied based on the principle
Changes in NOM characteristics due to the complexation of NOM-
developed by Serkiz and Perdue [18]. The detailed characteristics
metal ions are greatly inuenced by the type and alum dosage,
of the RO membrane and module used for concentrating the NOM
pH, ionic strength, NOM solubility and hydrodynamic condition,
sources are given elsewhere by Idris et al. [19] and the whole exper-
which contributed to the overall efciency of a coagulationUF
iment set-up is illustrated in Fig. 2, respectively. Moreover chemical
membrane process [1517]. In this study the coagulation process
properties of the feed stream solution was adjusted to the approx-
before membrane ltration was primarily employed to create sus-
imate value as the experimental designed requirement, by using
pended coagulated micro-ocs which were relatively bigger than
0.1N HCl, 0.1N NaOH and deionized water. The relationship between
the membrane molecular weight cut-off. Such approach was pre-
concentrations of Yong Peng NOM and its UV absorbance recorded
sumably effective in promoting higher NOM removal efciency
at 254 nm were plotted in standard curves as tabulated in Fig. 3.
through micro-oc cake layer rejection, thus would imply in
The slope of line (Fig. 3.) represents SUVA [3.38 L/(m mg)] which
coagulant dosage lower than the optimized level for aggregates
denotes an index of NOM relative aromaticity. In particular, SUVA
precipitation, reduce occulation retention time, increase mem-
is a function of humic fraction content within the NOM source and
brane owrate capacity, eliminate non-settleable ocs concerns
can be employed as the surrogate for the relative humic concen-
and could effectively reduce pore clogging by particles. Particu-
tration in the surface water. As can be inferred from Fig. 3 there
larly it was hypothesized that the hydrophobic fraction having
seems to appear a signicant correlation between humic fraction
more anionic binding sites than the hydrophilic fraction towards
and SUVA (R2 = 98.15%) which can be substituted for the relative
cationic aluminium hydrolysis product, was mainly contributing
humic fraction estimation by using UV and DOC measurements. The
in forming the micro-ocs via charge neutralization. In the case
SUVA value [3.38 L/(m mg)] was found consistent with the in situ
of hydrophilic fraction which has less electron-rich sites, was
SUVA of Yong Peng which was about 3.24 0.17 (Table 1). In gen-
supposed not participating in the charge neutralization with the
eral high SUVA possession could be correlated with greater NOM
aluminium hydrolysis product, thus apparently it was considered
aromaticity and negative charge density (Fig. 4) caused by the car-
playing only a minor role in forming the micro-ocs and in being
boxylic and phenolic moieties of hydrophobic acids [5], for NOM
associated with pore adsorption and poor removal by membrane
ltration. However with optimal setting of experimental factors
the hydrophilic fraction could be effectively removed through sur-
face adsorption on the neutralized occulant or entrapped within
the coagulated suspension, before being retained or absorbed on
the micro-oc cake layer that is formed on the membrane surface.
In particular a systematic experimental design based on full fac-
torial design was employed to determine the signicant effect of
pH, SUVA, FRT and alum towards NOM removal. A second level
design study was further conducted with central composite design
of response surface methodology to develop an empirical predic-
tive model of NOM removal and membrane permeability, based
on the signicant factors obtained from previous factorial design
study. In view of the fact that only a considerable amount of
research had been done, emphasis is placed towards quantitative
identication of signicant and interaction factors, and determi-
nation of the best setting of variable factors that produce the
Fig. 1. Apparent molecular weight distributions (AMWD) of Yong Peng NOM source
optimal outcome with respect to NOM removal and membrane water by UF fractionation using a series of cellulose acetate membranes with MWCOs
permeability. of 1 kDa, 5 kDa, 10 kDa and 30 kDa (Ultracel Millipore membrane).
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210 195

Table 2
DOC concentrations of NOM fractions for Yong Peng water (based on DOC and mass balance technique).

Source water Hydrophobic DOC (%) Transphilic DOC (%) Hydrophilic DOC (%) Unfractionated DOC (%) SUVA [L/(mg m)]

Yong Peng Intake 57 (3.05) 21 (1.12) 22 (1.17) 100 (5.34) 3.24

The numbers in parenthesis are DOC concentration in mg/L.

source which possessed higher SUVA was supposed to imply in

Fig. 2. Schematic diagram of concentration unit of RO membrane (1) feed; (2) valve;
(3) pump; (4) hollow ber pressure housing; (5) ow meter; (6) permeate; (7)
pressure gauge.
Fig. 3. Correlation curve of Yong Peng NOM concentration and its UV254 nm
absorbance.
greater NOM rejection due to higher coagulant demand towards
cationic aluminium (Al) hydrolysis and subsequently would pro-
duce micro-ocs of greater size. Thus SUVA factor was taken into
account in this study as one of the important factors since it was
relatively inuential in governing the NOM removal efciency in
the coagulation-submerged UF system. The spectrophotometric
behaviour of Yong Peng NOM was further studied as a function of
the pH solution (Fig. 5). It was shown that increase in solution pH
implied in increase in UV absorbance which directly increased the
SUVA, particularly at high pH values. This change in UV absorbance
with pH incremental is attributed to ionization (dissociation) of
hydrophobic NOMs carboxylic, hydroxyl and phenolic functional
groups which enhance the NOM intra-molecular repulsion [20,21],
thus subsequently increasing the NOM molecules solubility and its
degree of hydrophobicity. However, the inuence of pH on NOM
solubility may differ at low pH values. The fact that UV absorbance
decreases as the pH decreases is the supposition that at low pH val-
ues the ionizable functional groups of NOM are protonated, reduced
in electrostatic repulsion in between the NOM intra-chains, thereby
decreasing their solubility and followed by formation of coiled com-
plexes and more compacted NOM molecules conguration. These
uncharged complexes are less soluble and tend to agglomerate (due
to hydrophobicity interactions) before precipitated from solution.
Subsequently this condition resulted in lesser NOM residual, espe-
cially the hydrophobic NOM fraction, which is accompanied by
reduction in the UV absorption (shrinkage of the aromatic rings). It
is worth to note that results given in Figs. 35 are essentially use-
ful in correlating the membrane performance (NOM rejection and
ux rate) with the NOM feed characteristics, as the coagulationUF
system was operating at variety of pH and SUVA concentrations.
The relationship between higher UV absorbance at greater pH and
higher NOM charge density (mequiv./gC) were carefully considered
and would be used to elucidate the critical mechanisms involved
during coagulationocculationultraltration processes as well as
providing reasons for the coagulationUF system performances.

Fig. 4. The charge density per unit NOM mass of Yong Peng water by potentiometric
titration [milliequivalent per gram of Carbon from DOC measurement; mequiv./gC,
for carboxylic and phenolic groups of hydrophobic (HPO) fraction of NOM source Fig. 5. UV absorbance spectrophotometric characteristics of Yong Peng NOM as a
water]. function of pH values.
196 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210

Table 3
UF membrane specication.

Parameter PSF UF membrane

Membrane type Hollow ber

Membrane material Polysulfone
External diameter (m) 600
(Based on spinneret opening)
Internal diameter (m) 300
(Based on bore uid needle)
Contact angle ( ) 56
Zeta potential (mV @ pH 7) 27
MWCO 68 kDa
Pure water ux; Jpwf at TMP of 250 mmHg (L m2 h1 ) 13.7
Pure water permeability (L m2 h1 bar1 ) 43 5

al. [22]. Continuous feed supply controlled by a buoyant water

Fig. 6. Schematic diagram of the coagulationdirect UF system.
2.2. Submerged coagulationUF membrane
The experimental set-up is schematically illustrated in Fig. 6. The
system consists of rapid mix coagulation, occulation and direct
ultraltration without the need of sedimentation process. The UF
membrane characteristics, SEM images of clean membrane and
its zeta potential property are shown in Table 3, Figs. 7 and 8,
respectively. Details of the UF membrane fabrication process and
its properties determination procedure are given by Zularisam et
level controller was used to ensure sufcient loading of coagu-
lated NOM source into the process tank. Bubbling system controlled
by adjustable air ow regulator continuously supplied air bubbles
within the bers network at the bottom of membrane module to
provide a continuous up-ow circulation of micro-ocs suspen-
sion for hindering any micro-particles settlement. In particular
a constant air scouring bubble of 200 L/(m2 min) was applied to
exert shear stress to suppress potential particles deposition on
the membrane surface. A commercial alum of Al2 (SO4 )3 18H2 O
was employed throughout this experiment as it is widely used
in Malaysian water treatment plants. Final NOM source pH was
adjusted from 5 to 10 by addition of 0.1N NaOH and 0.1N HCl before

Fig. 7. SEM images of the cross section of clean asymmetric PSF membrane.
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210
Fig. 8. Zeta potential curves of PSF membrane by streaming potential technique.
coagulant mixing. The NOM source water spiked with the desired
coagulant dose was hydraulically pumped from the inuent tank
and over-owed into the process tank (Fig. 6). The owrate of the
coagulated NOM into the process tank was designed to range from
2.67 L/min to 8 L/min, which was technically equivalent to 15 min
and 5 min of occulation retention time (FRT), respectively. Floccu-
lation of feed water was done in the process tank according to the
designed FRT in order to maintain a rapid development of micro-
ocs (pin-sized ocs). A PSF hollow ber module with an effective
area of 0.11 m2 was immersed in the process tank and a constant
TMP (250 mmHg) was maintained to extract the occulated water
from the outside to inside of the membrane bers. The ux decline
would be expected to increase in the course of time due to mem-
brane fouling, thus operational permeate ux was monitored over
the time to determine the degree of membrane fouling to mem-
brane permeability. Parameters used to quantify the efciency of
membrane processes are ux (J), permeability and solute rejection
(R), where the ux is dened as
Q rejection rates are usually accompanied by low ux rates. The range
J=
A
where Q is the permeate owrate (L h1 ) and A is the membrane
area (m2 ) and permeability as
Q Q
Permeability = = (2)
AP NPdl
where Q is the permeate owrate (L h1 ), A is the effective mem-
brane area (m2 ), P is the transmembrane pressure (Pa), N is the
ber quantity, d is the membrane OD and l is the membrane effec-
tive length (m), the rejection (R%) as
  C 
p
R (%) = 1 100
Cf
where Cp is the permeate concentration in mg/L and Cf is the feed
DOC concentration (mg/L) measured by DOC analyzer (Shidmadzu
TOC-VE).
With optimal coagulant dosing, pH adjustment, appropriate
SUVA and proper FRT, the evolved suspended pin-sized ocs
(instead of settleable pin-sized ocs) could be effectively rejected
by the 68 kDa MWCO PSF membrane, resulting in higher NOM
removal with reasonable ux rate. This may also lead to lower
operating costs associated with lesser coagulant consumption and
sludge production, and shortened operation time as sedimentation
process was eliminated.
197
Table 4
Independent variables for rst order model (screening design).
Factors Unit Levels
1 +1
A (x1 ) Alum mg Al/L 1.8 3.0
B (x2 ) FRT min 5 15
C (x3 ) SUVA L/(m mg) 1.27 3.3
D (>x4 ) pH pH 5 10
2.3. Analysis of data
Full factorial design and central composite design were used
to quantitatively measure the signicant effect of variable factors
and their interactions with each other on the membrane perfor-
mance with respect to the NOM rejection efciency and relative
membrane permeability (responses). In addition, analysis of vari-
ance (ANOVA) was used to analyze data collected in the perspective
of the model adequacy corresponding to the signicance of the
regression model, signicance of individual model coefcients and
models lack of t possession. In fact experimental plan (at second
level design study) with the central composite design was used to
develop a prediction mathematical correlation model between the
signicant factors with respect to the optimum NOM rejection and
membrane permeability.
2.3.1. Full factorial design (rst order model)
Design Expert Software (Stat-Ease Inc., Statistic made easy, Min-
neapolis, MN, USA, version 6.04) was used for the experimental
design throughout this screening process study. A total of sixteen
sets of experiments (24 full factorial design) and three replicates
at the center point were used to demonstrate the statistical signif-
icance of the alum dosage (A; pretreatment), FRT (B; operational
condition), SUVA (C; NOM characteristic), and pH (D; solution
chemistry) on affecting the permeate quality. In this case DOC rejec-
tion was chosen to represent the quality characteristic performed
by the membrane as optimal conguration of operating conditions
was capable of achieving as close to a 100% rejection. A ux rate was
decided to be inappropriate as the quality characteristic since high
(1) and levels of the variables investigated in this study are shown in
Table 4 while Table 5 shows the experimental design and predicted
values of the screening process. Range settings for variable factors
were adjusted based on previous ndings and literature.
2.3.2. Response surface methodology (second order model)
The factorial design was further continued with the response
surface methodology (RSM) developed based on the central
composite design (CCD) with NOM removal and membrane per-
meability as the dependent variables (responses) while signicant
term from preliminary screening process were chosen as the inde-
pendent factors. The CCD was conducted with a 23 full factorial
central composite design of combinations factors at two levels
(3) (high, +1 and low, 1 levels), included with six star points (axial)
corresponding to an value of 2 and six replicates at the center
points (coded level 0, midpoint of high and low levels). In this
design, due to their relative insignicancies for NOM removal, the
FRT duration and aeration intensity were set at its center point set-
ting (10 min) and 200 L/(m2 min), respectively. The range and levels
of the processing parameters involved are tabulated in Table 6 while
the central composite design matrices and experimental response
of each individual experiment are shown in Table 7. In this study
the independent variable for pH is represented by variable A while
SUVA and alum by B and C, respectively. In this design, the FRT fac-
tor was constantly set at the center point settings (10 min) as it was
found to be insignicances in the organic removal (Table 8).
198 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210

Table 5
Experimental design and results of 24 full factorial design.

Standard Run Block Coded factors NOM removal (%DOC)

Alum FRT SUVA pH Experiment Predicted

x1 x2 x3 x4

1 16 {1} 1.0 1.0 1.0 1.0 30.42 32.49

2 19 {1} 1.0 1.0 1.0 1.0 57.00 55.61
3 11 {1} 1.0 1.0 1.0 1.0 43.6 41.66
4 13 {1} 1.0 1.0 1.0 1.0 48.0 49.27
5 3 {1} 1.0 1.0 1.0 1.0 50.1 49.21
6 6 {1} 1.0 1.0 1.0 1.0 61.17 61.38
7 18 {1} 1.0 1.0 1.0 1.0 62.9 63.67
8 1 {1} 1.0 1.0 1.0 1.0 60.42 60.33
9 14 {1} 1.0 1.0 1.0 1.0 48.23 46.62
10 4 {1} 1.0 1.0 1.0 1.0 73.6 74.54
11 12 {1} 1.0 1.0 1.0 1.0 50.28 51.77
12 10 {1} 1.0 1.0 1.0 1.0 65.0 64.18
13 17 {1} 1.0 1.0 1.0 1.0 40.3 40.74
14 9 {1} 1.0 1.0 1.0 1.0 57.47 57.71
15 7 {1} 1.0 1.0 1.0 1.0 51.5 57.17
16 2 {1} 1.0 1.0 1.0 1.0 53.0 51.18
17 5 {1} 0.0 0.0 0.0 0.0 57.4 52.64
18 15 {1} 0.0 0.0 0.0 0.0 55.8 57.17
19 8 {1} 0.0 0.0 0.0 0.0 58.3 57.17

Table 6 ware 6.0.4 was used to develop the experimental plan and optimize
Independent variables and concentration levels for response surface study.
the regression equation (Eq. (4)). The statistical signicance of
Factors Unit Levels the second order model equation was determined by performing
2 1 0 +1 +2 Fishers statistical test for analysis of variance (ANOVA). In particu-
lar a good model must be signicant based on F-value and P-value as
A (>x1 ) pH pH 2.5 5 7.5 10 12.5
B (>x2 ) SUVA L/m mg 0.26 1.27 2.29 3.3 4.31
opposed to the Lack of Fit (insignicant). Moreover the proportion
C (x3 ) Alum mg Al/L 1.2 1.8 2.4 3 3.6 of variance exhibited by the multiple coefcient of determination
R2 should be close to 1 as this would demonstrate better correlation
= 2.
between the experimental and the predicted values.

The quadratic model for predicting the optimal point was

3. Results and discussion
according to Eq. (4).
  
Y = b0 + bi xi + bii xi 2 + bij xi xj (4) 3.1. Factorial design

where Y is the response variable, b is the regression coef-
cient of the model, x is the coded levels of the independent
variables.
In general primary objective of RSM is to optimize the response
(Y) based on the factors investigated [23]. The Design Expert soft-
Analysis of experimental data by a complete 24 factorial design
was systematically conducted as an initial screening process by
examining the effects and interactions of pH, SUVA, FRT and alum
dose on NOM removal of ltered Yong Peng NOM source, as sum-
marized in Table 5. A statistical testing using Fishers statistical test

Table 7
Experimental layout and results of 23 full factorial central composite design.

Standard Run Block Factor variables Responses

pH x1 SUVA x2 Alum x3 NOM removal (%) Permeability LMHBar

1 9 1 5.00 1.27 1.80 44.70 17.33

2 11 1 10.00 1.27 1.80 66.30 8.70
3 5 1 5.00 3.30 1.80 55.20 9.70
4 6 1 10.00 3.30 1.80 46.50 13.75
5 8 1 5.00 1.27 3.00 50.10 27.09
6 3 1 10.00 1.27 3.00 74.60 12.00
7 7 1 5.00 3.30 3.00 82.70 32.08
8 12 1 10.00 3.30 3.00 74.60 28.30
9 2 1 2.50 2.29 2.40 54.20 22.03
10 19 1 12.50 2.29 2.40 75.80 8.66
11 10 1 7.50 0.26 2.40 56.50 26.10
12 13 1 7.50 4.31 2.40 77.10 32.10
13 4 1 7.50 2.29 1.20 45.30 9.53
14 16 1 7.50 2.29 3.60 79.70 22.39
15 20 1 7.50 2.29 2.40 58.00 23.10
16 17 1 7.50 2.29 2.40 56.00 24.90
17 15 1 7.50 2.29 2.40 62.00 28.10
18 14 1 7.50 2.29 2.40 56.00 23.48
19 1 1 7.50 2.29 2.40 58.00 28.80
20 18 1 7.50 2.29 2.40 60.00 25.00
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210 199

Table 8
ANOVA for 24 full factorial design; response: NOM removal (%).

Source Sum of Squares DF Mean squares F-value Prob > F

Model 1628.07 10 162.81 49.36 <0.0001a

A 604.32 1 600.25 183.23 <0.0001

B 16.83 1 16.83 5.10 0.0584
C 26.86 1 26.86 8.14 0.0246
D 41.50 1 41.50 12.58 0.0094
AB 240.65 1 240.65 72.96 <0.0001
AC 119.95 1 119.95 36.37 0.0005
AD 23.01 1 23.01 6.98 0.0334
BC 27.95 1 27.95 8.47 0.0226
BD 16.10 1 16.10 4.88 0.0629
CD 510.90 1 510.90 54.90 <0.0001

Residual 3.09 7 3.30

Lack of Fit 19.88 5 3.98 2.48 0.3119b

Pure Error 3.21 2 1.60

Cor Total 1688.69 18

Std. Dev. 1.82 R2 0.9860

Mean 53.92 Adjusted R2 0.9660

Values of Prob > F less than 0.0500 indicate model terms are signicant.
a
Signicant.
b
Not signicant.

for ANOVA was employed for the determination of signicant vari- ogy effects, as addition of coagulation dose is presumably effective
ables where degree of signicance was ranked based on the value in shifting towards larger physical size of coagulated suspension
of F-ratio. As matter of fact the larger the magnitude of F-value and consequently may result in greater water treatability either
and correspondingly the smaller the Prob > F value, the more by adsorbing on the membrane surface through molecular attrac-
signicant are the corresponding model and the individual coef- tion (van der Waals or London forces) or effectively rejected by
cient [23]. It was observed from ANOVA analysis (Table 8) that steric hindrance prior to back transporting away from the mem-
the condence level was greater than 95% (P < 0.05) for removal brane surface (to bulk water). Such condition could apparently lead
efciency while F-value and P-value of the model were 49.36 and to formation of cake deposition of charged neutralized occulant
0.0001 respectively, thus indicating that the estimated model ts and/or aluminium hydroxide precipitate on the membrane sur-
the experimental data adequately. Furthermore the coefcient of face. This particles deposition in response acts as a lter media,
determination R2 of the model was reasonably close to 1 (0.98), reducing the effective molecular cut-off (MWCO) of the UF mem-
implying that about 98% of the variability in the data was explained brane, and thus improving the NOM removal. Apparently results of
by the model. It was further shown that the main effect of alum (A), Fig. 10a essentially depicting that an increase in coagulant dosage
pH (D), SUVA (C) and the two level interactions of AB, AC, AD, BC at high pH application, tends to widen the range of optimum coag-
and CD were signicant model terms (factors). Other model terms ulant dosage, but not optimum pH, with respect to maximum NOM
especially the main effect of FRT (B) was relatively less signicant in removal. However coagulant overdosing is not desirable as it could
inuencing NOM removal as their condence level were less than present high residual metal concentration, substantial operation
95% (P > 0.05). costs and problems related to sludge production.
Signicances of effects and interactions of factors on a response On the other hand, increasing the alum dose at the minimum
were further diagnosed and compared, and graphically illustrated pH level (pH 5; Fig. 10a) appeared to have only minor effects on the
in the half normal plot (Fig. 9), where results of dominating effects
that are likely to represent the important and inuential factors
were found consistent with the ANOVA analysis results. Moreover
the signicance of interactions between factors on the response
can be best considered using interaction analysis graph of Fig. 10. It
has been observed that the interaction effect between alum and pH
(Fig. 10a) depicts a remarkable improvement in NOM removal ef-
ciency as the alum dose increases from minimal to maximum level,
suggesting that this variable signicantly affect the NOM removal.
The enhancement brought by increasing alum dose appears to be
greater at higher pH condition (pH 10), which is signicantly con-
trary to the results presented in Fig. 10b. Incremental of water pH
increases charge density and the UV254 absorbance (Figs. 4 and 5)
as a result of ionization of the negatively charged functional groups
that increased intra-molecular repulsion and NOM solubility, pri-
marily the hydrophobic compounds. The dissociation of these
functional groups creates large demand on the positively charged
coagulant, and as alum dose increased more Al hydrolysis species
were available to neutralize the negatively charged sites of acidic
NOM. It is anticipated that higher DOC removal at greater alum
dose was due to the micro-ocs characteristics and cake morphol- Fig. 9. The half normal plot for 24 full factorial designs.
200 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210
Fig. 10. Plot of interaction effect for NOM removal (%DOC): (a1 and a2) effect between alum and pH, (b1 and b2) effect between SUVA and pH.
extent of NOM removal despite conducting the experiment in the
charge neutralization condition (pH 5). This observation could be
explained due to the insufcient anionic NOMs that were available
for charge neutralization with the increasing cationic aluminium,
as low pH condition corresponded to less negatively charge (Fig. 4)
and more insoluble humic/fulvic acid [24]. In other word dissoci-
ation of NOM is limited at low pH and the neutralization by the
positively charged coagulant has little effect. Furthermore results
of this study also revealed that coagulation prior to direct ultra-
ltration was not only responsible for the removal of high charge
density (presence of carboxylic groups) and high molecular weight
(MW) hydrophobic fraction, such as humic/fulvic acids, but also
capable of removing some lower MW and non-ionic (low charge
density) hydrophilic compounds which were poorly removed by
the conventional coagulation process [2,6,9,25]. This was evident
from the results of Run 4 and Run 6 (Table 5) which demon-
strated outstanding NOM removal (73.60% and 61.17%, respectively)
despite of having total hydrophobic NOM fraction of only 57%
(Table 2). Surprisingly both results were corresponding to FRT of
minimum level (5 min), suggesting that within this shortest oc-
culation time, the micro-ocs have already grown large enough to
be excluded by the membrane. This nding suggests that the inte-
grated UF membrane process with precoagulation, removed NOM
substances more efciently than results previously reported by Qin
et al. [26] (59.5%), Xia et al. [27] (47%) and Kabsch-Korbutowicz et
al. [28] (66.2%). However experiment done by Pikkarainen et al.
[29] indicated maximum TOC removal that amounted to 78% but
this result was obtained with metal salt coagulant of higher dose.
Other researchers reported similar observations, i.e. the specic
cake resistance was decreasing while TOC removal was increas-
ing, with increasing dosage of coagulants [10,28,30]. In the case
of interaction effect between SUVA and pH (Fig. 10b), increasing
SUVA from 1.27 (L/m mg) to 3.30 L/(m mg) improved NOM removal
linearly at the low pH level (pH 5), however under identical SUVA
conditions, opposite results were obtained at the high pH level (pH
10). This observation signicantly demonstrated that the efciency
of coagulationultraltration process is reasonably controlled not
only by pore size exclusion but also by solution chemistry (pH
dependent), in addition to SUVA parameter. This could be explained
by the fact that DOC removal by membrane exclusion is higher in
the charge neutralization coagulation pH zone (pH 5.06.5) than
that under the condition of sweep coagulation condition (pH > 6.5)
[31,32]. Primarily due to the negative charge carried by NOM, there
is a stoichiometric relationship among the required coagulant dose,
solution conditions such as pH and the TOC concentration in the
water to be treated [33]. This supposition is consistent with Yong
Pengs NOM composition which mainly comprised hydrophobic
fraction (57%), carrying sufcient anionic binding sites that created
more coagulant demand with the cationic aluminium hydrolysis
as the SUVA is increased (due to dissociation of carboxylic and
hydroxyl functional groups) [Eq. (5)]. In particular this condition
was promoting formation of greater physical size of micro-ocs
of metalhumic/fulvic complexes via charge neutralization mecha-
nism that was more effectively removed by membrane ltration. In
other words as the relative fraction of humic/fulvic increases with
increasing SUVA, contribution of the charge neutralization to NOM
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210 201

removal increased, especially when the applied pH was closed to
the isoelectric point (IEP) of Al(OH)3 (s) [34]. On the other hand
at pH greater than 6.5, the insoluble aluminium hydroxide crys-
tals dominate in water, contribution of the charge neutralization
decreased and micro-ocs formation process is eventually depen-
dent on the adsorption of hydrophobic/hydrophilic substances
on the amorphous solid-phase Al(OH)3 (s) [Eq. (6)]. Subsequent
surface adsorption followed by sweep coagulation (conventional
entrapment) is presumed to generate micro-ocs of inadequate
size, insufciently large to be rejected neither by the cake layer
nor by membrane pores. This hypothesize is in good accordance
with previous studies which reported lower NOM removal rate by
precipitation occurred particularly at higher pH (pH > 5.5) due to
insufcient oc density, implying that the formed micro-ocs were
of smaller size [13,26,29].
Al(OH)n 3n + HPO NOMx Al(OH)n HPO NOM
(soluble complex)
Al(OH)n HPO NOM(s)
(solid)
Al(OH)n 3n + HPO/HPI NOMx HPO/HPI NOM Al(OH)3 (s)
(adsorbed)
In another perspective, decrease in NOM removal with an
increase in SUVA at pH 10 (Fig. 10b), is attributable to the molecular
structure of humic/fulvic which varies from rigid spherocolloidal
or compacted conguration (at low pH) to exible linear macro-
molecules (at alkaline pH range) [17,21]. Being a linear shape
conguration with more soluble compound enables easier passage
of NOM macromolecule through membrane pores without being
excluded by steric exclusion. Conversely, possibility relating to high
NOM removal at low pH level could be well corresponded to the
membrane matrix (change in membrane pore size), which is a func-
tion of solution chemistry. Braghetta et al. [24] claimed that low pH
condition attributed to compaction of membrane matrix or pore
size that restricts the entrance of solute through the membrane.
This was reasoned due to reduction in electrostatic charge repul-
sion or charge neutralization at the membrane surface followed by
electric double layer compression that distinctively caused com-
paction of membrane pore volume, thus considerably responsible
in implying high detainment of organic solutes. It has also been
observed that reduction in electrostatic charge repulsion as pH
decreased, has enhanced humic acid rejection by adsorbing more
densely on membrane surface, which signicantly corresponded to
a less negatively charged membrane, less negatively charged humic
acid and more insoluble humic material [35,36]. Fig. 10b demon-
strated the importance of SUVA and the optimum pH range with
respect to maximum NOM removal and as well as denoting the
inter-relationship between the coagulation conditions towards the
relative concentration of NOM composition. It was noticeable that
the relative NOM composition has turned out to be the optimal
pH range-determining factor with regards to process performance
efciency. In particular the charge neutralization coagulation (at
low pH level) appeared to be relatively more signicant for NOM
source predominated with hydrophobic fraction such as at the high
SUVA level (+1), owing to the charge interactions, whereas sweep
coagulation mechanism (at high pH level) through surface adsorp-
tion was more favorable for low SUVA NOM source (1), which was
primarily occupied by less negatively charged of non-humic NOM.
(5) This notation was in good accordance with results of Fig. 10b which
depicted maximum organic removal only to occur at low pH level
(pH 5) and at high SUVA (3.30 L/(m mg)), whereas under high pH
level (pH 10) maximum NOM removal was corresponded with low
(6) SUVA (1.27 L/(m mg)).
Apart of that the regression model obtained from the factorial
design analyses can be as well adopted in screening the crucial and
critical variable of operating conditions. A variable is claimed to
have greater signicant effect on NOM removal if its coefcient was
relatively larger than the others whereas the variable with positive
tted constant, has an enhancer effect towards NOM removal com-
pared to negative coefcient which had opposite effect. As can be
inferred from Eq. (7), which includes the coefcient for each effect,
the main effect of alum dose (A) has the largest coefcient (+6.15)
followed by pH (D, +1.61), SUVA (C, +1.30) and FRT (B, +1.03). Appar-
ently this result was consistent with ANOVA analysis in Table 8
where the alum dose (A) variable is shown to have the highest F
value.
NOM removal = 53.31 + 6.15(A) + 1.03(B) + 1.30(C) + 1.61(D)
3.88(A B) (%DOC)2.74(A C) + 1.20(A D)
+1.32(B C) 1.00(B D) 5.65(C D) (7)

Table 9
ANOVA for Response Surface Quadratic Model [Partial sum of squares] Response: NOM removal (%).

Source Sum of squares DF Mean squares F-value Prob > F

Model 2631.64 9 292.40 43.18 <0.0001a

A 328.52 1 328.52 48.51 <0.0001

B 260.02 1 260.02 38.39 0.0001
C 1191.98 1 1191.98 176.00 <0.0001
A2 60.14 1 60.14 8.88 0.0138
B2 100.23 1 100.23 14.80 0.0032
C2 21.35 1 21.35 3.15 0.1062
AB 494.55 1 494.55 73.02 <0.0001
AC 1.53 1 1.53 0.23 0.6446
BC 219.45 1 219.45 32.40 0.0002

Residual 67.72 10 6.77

Lack of Fit 40.39 5 8.08 1.48 0.3394b

Pure Error 27.33 5 5.47

Cor. Total 2699.37 19

Std. Dev. 2.60 R2 0.9749

Mean 61.66 Adjusted R2 0.9523

Values of Prob > F less than 0.0500 indicate model terms are signicant.
a
Signicant.
b
Not signicant.
202 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210
3.2. Response surface methodology (RSM)
The three signicant variables alum dosage, pH and SUVA were
further optimized using response surface methodology and results
on the effect of variable factors towards NOM removal, one of
the response variables, are shown in Table 9. In this design, the
FRT factor was set at the center point settings (10 min) due to its
low signicances for organic removal (from Table 8) while aer-
ation intensity was maintained at 200 L/(m2 min). Fit summary
output analysis indicated that the quadratic model was statisti-
cally signicant to represent both the NOM removal and membrane
permeability responses. The adequacy of a quadratic model was
examined by F test, Prob > F and the determination coefcient R2 .
As can be inferred in Table 9, the computed F and Prob > F were
43.18 and <0.0001, respectively, which implied that the model was
highly signicant with low probability. Results obtained adequately
suggesting that the present mathematical model was in good pre-
diction of the experimental results and as a matter of fact the terms
in the model have a signicant effect on the response. In a similar
manner, the multiple correlation coefcient of R2 was calculated to
be 0.9749, indicating a good agreement existed between the exper-
imental and predicted value as well as depicting that 97.49% of the
variability in the response could be well explained by the model
while only 2.51% of the total variation was poorly described by the
model. Moreover the Lack of Fit value was found insignicant
(Prob > F = 0.3394) which denoted that the model was desirably t.
The main effect of alum dose (C) was found to be the most signif-
icant factor to have the largest effect towards the NOM removal
efciency and this was followed by the two level interactions of pH
and SUVA (AB), and the main effect of pH (A). Moreover the main
effect of SUVA (B), the two level interactions between SUVA and
alum dose (BC), the second order effect of SUVA (B2 ) and the sec-
ond order effect of pH (A2 ) were found to be responsible for the
secondary effect on the NOM removal.
The relative effect of alum dose as operating parameter on
NOM removal and membrane permeability was clearly visible since
experiments operated at low alum dose level (1 and 2; Runs 4, 9,
11) exhibited some of the lowest organic removal and membrane
permeability. It is further shown that at lower pH level (1), an
increase of removal efciency has been observed, with maximum
%DOC removal (82.70%) was found to occur at pH 5.0 (Run 7), on
the other hand the membrane permeability showed dependent on
the coagulation condition, being higher at the charge neutraliza-
tion pH zone (pH 5) than for the sweep-oc condition (Run 19). An
Table 10
ANOVA for Response Surface ReducedQuadratic Model [Partial sum of squares] Response: NOM removal (%).
Source Sum of Squares
Model 2608.76
A 328.52
B 260.02
C 1191.98
A2 47.96
B2 85.30
AB 494.55
BC 219.45
Residual 90.61
Lack of Fit 63.28
Pure Error 27.33
Cor. Total 2699.37
Std. Dev. 2.75
Mean 61.66
Values of Prob > F less than 0.0500 indicate model terms are signicant.
a
Signicant.
b
Not signicant.
inverse relationship between organic removals and membrane per-
meability, in the case of sweep-oc condition (Runs with pH > 6.5),
suggested that the lower membrane permeability was considerably
attributed to the formation of less porous and more compressible
cake compared to those of the charge neutralization condition. It
was also observed that the removal efciency seemed to decrease
noticeably when higher pH was employed (Run 19 and Run 20)
despite fairly high alum dose and SUVA were used in the experi-
ments. In conjunction, this observation corresponded as evidence
to results obtained from Fig. 5, which explained the relationship
between the increases in UV254 nm absorbance with increasing pH
value. Apparently this phenomenon could be well explained due
to the fact that, NOM solubility and SUVA would be increasing
proportionally with the pH increment as more functional groups
were ionized including the charged acidic groups such as carboxylic
and phenolic. Such condition greatly increases the acidic charged
density (Fig. 4) and the electrostatic repulsion between the NOM
intra-chains, resulted in the formation of exible linear congu-
ration of NOM molecules, which were more soluble. Ionization of
NOM molecules enable easier passage through membrane pores,
concomitantly reduced most of the acidic/charged NOM partic-
ularly the hydrophobic fraction and eventually left only soluble
hydrophilic NOM which has less electron-rich sites or insufcient
anionic binding sites towards the cationic aluminium hydrolysis
product [5,24]. Subsequently this phenomenon attributed to for-
mation of relatively inadequate micro-ocs size via poor surface
adsorption onto the insoluble Al(OH)3 (s) amorphous solid-phase,
which was ineffectively retained by the membrane pore size. This
condition has therefore resulted in low NOM removal with slightly
improved ux rate as portion of the NOM solute could easily passing
through the membrane pores.
It should also be noted that other model terms such as the sec-
ond order effect of alum (C2 ) and the two level interactions of the
pH and alum (AC) were found insignicant (Prob > F more than
0.0500 indicate model terms are insignicant) and therefore can be
eliminated for model improvement (Reduced Quadratic Model). In
conjunction, the backward elimination procedure was employed to
eradicate the insignicant terms and ANOVA results of this reduced
quadratic model is tabulated in Table 10. The results revealed that
the model signicacy was improved (F = 49.36 instead of 43.18 for
previous model) with alum dose (C) appeared as the primary main
effect contributor followed by the two level interactions of pH and
SUVA (AB), main effect of pH (A), SUVA (B), the two level inter-
action of BC, the second order effect of B2 and A2 . Hence in this
DF Mean squares F-value Prob > F
7 372.68 49.36 <0.0001a
1 328.52 43.51 <0.0001
1 260.02 34.44 0.0001
1 1191.98 157.86 <0.0001
1 47.96 6.35 0.0269
1 85.30 11.30 0.0057
1 494.55 65.50 <0.0001
1 219.45 29.06 0.0002
12 13.89
7 9.04 1.65 0.2998b
5 5.47
19
R2 0.9664
Adjusted R2 0.9469
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210 203

Table 11
ANOVA for Response SurfaceReducedQuadratic Model [Partial sum of squares] Response: Membrane permebility (LMHBar).

Source Sum of squares DF Mean squares F-value Prob > F

Model 1087.81 7 155.40 13.33 <0.0001a

A 157.44 1 157.44 13.50 <0.0032

B 58.94 1 58.94 5.06 0.0441
C 358.25 1 358.25 30.72 0.0001
A2 229.23 1 229.23 19.66 0.0008
AB 71.94 1 71.94 6.17 0.0288
BC 71.22 1 71.22 6.11 0.0294

Residual 139.93 12 11.66

Lack of Fit 111.85 7 15.98 2.85 0.1337b

Pure Error 28.08 5 5.62

Cor Total 1227.73 19

Std. Dev. 3.41 R2 0.8860

Mean 21.16 Adjusted R2 0.8195

Values of Prob > F less than 0.0500 indicate model terms are signicant.
a
Signicant.
b
Not signicant.

study the ranking is as follows: C > AB > A > B > BC > B2 > A2 . In the
case of membrane permeability as the second response variable,
the backwards elimination procedure was also selected for model
improvement (Table 11). The main effect of alum dosage (C), the
second order effect of pH (A2 ), the second order effect of alum
(C2 ), the main effect of pH (A), the two level interaction of AB, the
two level interaction of BC and main effect of SUVA (B) are sig-
nicant model terms for membrane permeability, thus the ranking
according to the model term signicacy (based on the magnitude of
F-value) is C > A2 > C2 > A > AB > BC > B. The co-efccient of determi-
nation R2 for membrane permeability was 0.8860 indicating good
correlation existed between the experimental and predicted values.
The multiple regression equations for NOM removal and mem-
brane permeability using pH (A), SUVA (B) and alum (C) as the main
variable were as follows:
Final empirical model in terms of coded factors:
NOM removal = +59.15 + 4.53 A + 4.03 B + 8.63 C
+ 1.35 A2 + 1.80 B2 7.86 A B
+ 5.24 B C
Permeability = +25.75 3.14 A + 1.92 B + 4.73 C 2.95
A2 2.80 C 2 + 3.00A B + 2.98 B C
Final empirical model in terms of actual factors:
NOM removal = +17.2747 + 5.65477 pH 1.41051 SUVA
5.26596 Alum + 0.21586 pH2 + 1.74632
SUVA2 3.09852 pH SUVA + 8.60016
SUVA Alum
Permeability = 12.23 + (3.12 pH) (18.73 SUVA)
+ (33.96 Alum) (0.47 pH2 ) (7.76 Alum2 )
+ 1.18 pH SUVA + 4.89 SUVA Alum
The above empirical model equations are mathematical corre-
lation model that can be employed to predict and optimize the
NOM removal and membrane permeability within the range of
variable factors of this experiment. Analyses on normal probability
plot of the residuals (Fig. 11) depicted nearly a straight line residu-
als distribution, which denoting errors are evenly distributed and
therefore support adequacy of the least-square t, while results
illustrated in Fig. 12 revealed that the models proposed are dis-
tinctively adequate and reasonably free from any violation of the
independence or constant variance assumption, as studentized
residuals are equally tabulated within the red line of the x-axis.
The effect of pH, SUVA and alum dose process variables on NOM
removal and membrane permeability was further analyzed using
simulated three dimensional response surface and contour plots
according to the backward quadratic model. The effect of pH and
SUVA on NOM removal depicted in Fig. 13 demonstrated that the
NOM removal increased when pH changed from 10.0 to 5.0 and as
SUVA concentration increased from 1.27 to 3.30. Based on the result,
the maximum removal of 69.65% is obtained when pH and SUVA is
5.0 and 3.3, respectively. In addition, the change of organic removal
was further analyzed as a function of alum dose and pH (Fig. 14).
It should be noted that alum dose affects NOM removal in a linear
(8) way as the pH, where removal efciency is found maximum at high
level factor (+1). In fact the slope of the increase is dependent on
pH and alum dose, and appears to be gradually steep at higher level
conditions. It is worth to note that increase in pH at high alum level
(3.0 mg/L), resulted in increase of NOM removal, however lower
(9) organic removal was applied at low level of alum dose (1.8 mg/L),
suggesting that the performance of process applied was essentially
inuenced by alum variable. Results of Figs. 13 and 14 were found
to be consistent with ndings of Fig. 10 that demonstrated alum
dose provided the principle effect to NOM removal in addition to
pH and SUVA variable factors.
The surface and contour plots of the effect of SUVA and pH on
membrane permeability while keeping alum dose at the middle
level (2.40 mg Al/L), is shown in Fig. 15. It was clearly shown that the
(10) decrement of membrane permeability was apparently monotonous
with the increase of SUVA, where the membrane permeability
decreased from 27.01 L m2 h1 bar1 at SUVA of 1.27 L m 1 mg1
to 24.04 L m2 h1 bar1 at SUVA of 3.30 L m1 mg1 when pH
was constantly maintained at 5.0. Conversely, opposite result was
observed with the high pH level (pH 10), in which the membrane
(11) permeability was increasing from 14.73 L m2 h1 bar1 at SUVA of
1.27 L m1 mg1 to 24.55 L m2 h1 bar1 (SUVA of 3.3 L m1 mg1 )
when alum dose was applied at the centre point of 2.40 mg Al/L.
Apparently membrane permeability was varied with the oper-
204 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210

Fig. 11. Normal probability plot of residual for (a) NOM removal and (b) membrane permeability.

ational pH conditions as the SUVA was increased. Lower pH
condition led to lower membrane permeability, while higher pH,
enlarged the permeability to some extent. It is reasonable to
suppose that with increasing SUVA from 1.27 to 3.3 L m1 mg1 ,
specically at the low pH level, contribution of the charge neu-
tralization predominated for micro-oc formation of relatively
sufcient size for steric hindrance. Hence allowing the coagulated
suspension to accumulate densely in the form of cake layer at
the membrane surface and to the extent of impeding permeate
ow despite improved organic solute rejection. In the case of bet-
ter membrane permeability shown at the high pH level, could be
closely related to the micro-oc formation of relatively insuf-
cient size to be effectively retained or presumably attributed to
the formation of more porous cake with the sweep-oc condition.
Besides that the effect of pH and alum dose on membrane perme-
ability is presented in Fig. 16. It can be seen that the maximum
membrane permeability of 27.87 L m2 h1 bar1 corresponded in
negative correlation with the pH but in opposite manner with
the alum dose. In particular the membrane permeability increased
when pH was decreased from 10.0 to 5.0 and as alum dose con-
centration was increased from 1.8 mg Al/L to 3.0 mg Al/L (Fig. 16a).
Higher membrane permeability at low pH, as alum is increased
(Fig. 16b), than at the high pH level suggested that excessive alum
addition was not favorable as it could lead to insignicant NOM
rejection (Fig. 10a) due to inefcient charge neutralization process.
Low pH condition reduced solubility and charge density of acidic
NOM, and in the case of constant SUVA concentration (Fig. 16), alum
addition would only result in formation of immature micro-oc
which potentially managed to pass through the membrane pores,
thus implying in high water permeability.

Fig. 12. Plot of residual against predicted response (a) NOM removal and (b) membrane permeability.
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210 205

Fig. 13. Interaction graph (a) and contour plot (b) of NOM removal from the model equation: effect of SUVA and pH.

In general NOM source water contained humic (hydrophobic
acids) and non-humic (hydrophilic) fractions distribution with the
hydrophobic NOM possessed higher contents of acidic functional
groups, while the hydrophilic fraction is consisted of none [5,37,38]
or lesser ionizable functional groups (due to transphilic NOM).
Therefore better NOM rejection by NOM source of higher SUVA
or source water which contained relatively greater hydrophobic
fraction could be explained due to reactivities difference of NOM
components towards cationic aluminium hydrolysis products. In
particular the hydrophobic NOM fraction has more electron-rich
sites (anionic binding sites) than with the hydrophilic compo-
nents, thus attributed to better agglomeration of bulk NOM through
charge neutralization with the cationic aluminium hydrolysis. Sub-
sequently better result of NOM agglomeration would then implied
in bigger micro-ocs and greater DOC rejection as the evolved
charge neutralized occulant contributes to cake formation of
higher dynamic permeability, less denser, lower hydraulic resis-
tance and more compressible, as illustrated in Fig. 17a. Note
that in Fig. 4, the charge density of hydrophobic NOM frac-
tion appeared to be substantially greater than the hydrophilic
fraction, thus essentially suggesting that the hydrophobic frac-
tion contained relatively higher ionizable groups per unit organic
carbon or had more anionic binding sites than the hydrophilic
portion [22,39]. Moreover this observation was well supported
by statement of Altmann and Ripperger [40] who claimed that
it was more difcult for large particles to foul the membrane

Fig. 14. Interaction graph (a) and contour plot (b) of NOM removal from the model equation: effect of pH and alum dose.
206 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210
Fig. 15. Interaction graph (a) and contour plot (b) of membrane permeability from the model equation: effect of SUVA and pH.
surface than smaller particulate. In fact this supposition could
be closely correlated with the Kozeny equation [Eq. (12)] that
expresses the specic resistance (Rc ) of incompressible cake. Based
on this equation, the cake specic resistance increases when the
diameter of deposited particles (dp ) decreases in size, thus appar-
ently resulting in higher hydraulic resistance of cake formation
[41].
180(1 c )2
Rc = 2
(12)
dp c 3
where is the porosity of gel and dp is the diameter of particle
deposited.
In addition it was also suppose that the residual NOM of charged
acidic groups, which were not participating in the charge neu-
tralization, was effectively rejected by the negative charge of PSF
membrane surface (pH 5; 18 mV), thus eventually attributed to
higher NOM removal. In contrast, ltration of NOM source with
lower SUVA (less charge density) was found to experience greater
ux decline and lesser NOM removal despite lower hydrophobicity
interactions with the hydrophobic PSF membrane. This observa-
tion could be explained by the fact that NOM of low SUVA has
lesser electrostatic attraction and minimal coagulant demand than
NOM of high SUVA, therefore it (NOM of low SUVA) was appar-
ently favourable in becoming smaller micro-ocs due to inefcient
binding process between COO or OH of NOM and the hydrolyze
Al3+ and consequently the ocs were poorly pore excluded. It
is worth to note that during early dissociation of aluminium
salts, soluble hydrolysis species will bind with negative charge
carried by NOM such as phenolic and carboxylic groups [6,13].
However due to poor charge neutralization (insufcient anionic
binding sites), the unreacted aluminium salts which were not neu-
tralized or existed as residual aluminium (exceeded solubility)
during aluminium hydrolysis reaction were converted into insolu-
ble aluminium hydroxides. Subsequently the insoluble aluminium
hydrolysis products possessing of charged neutralized occulant
and aluminium hydroxides would adsorb, entrap and sweep the
suspended NOM of relatively higher hydrophilic fraction which
has smaller SUVA possession and lower repulsion toward the oc-
culant. Moreover micro-ocs with prematured size (inadequate
size) especially with the sweep-oc condition (pH > 6.5) has con-
siderably low settle ability problem (requires high FRT) and was
merely detrimental to the effective membrane permeability (mem-
brane pores permeability) as it involved combination of adsorption
on membrane pore matrix and to the extent of pore constriction
within the membrane pore structure, as illustrated in Fig. 17b. Sub-
sequently NOM component that was relatively smaller than the
membrane MWCO, could easily passing through the membrane
pore opening hence implying in low NOM removal and poor perme-
ate ux quality. Therefore possession of high SUVA property in NOM
source is preferable as it could essentially inuenced the possibility
of charge neutralization mechanism, instead of sweep coagulation,
which was noticeably responsible in changing the ocs morpholog-
ical characteristic (bigger pin-sized ocs), thus implying in lower
hydraulic resistance, greater NOM removal and as well as better
membrane permeability (Fig. 17a). However inappropriate alum
dosage application despite moderately high SUVA possession, as
in the case of Standard order 13 (Run 4), could correspond to oppo-
site results and worse membrane ltration performance (permeate
ux parameter) considerably due to adsorption fouling mech-
anism (induced by hydrophobicity interactions) and rapid ux
decline.
3.2.1. Validation of empirical model adequacy
Adequacy of the developed empirical model needs to be ver-
ied or validated in order to conrm the prediction accuracy,
which is generated by the regression equation in predicting the
removal efciency and membrane permeability at any particular
pH, SUVA and alum within the range of level dened previously.
Experimental rechecking was performed using conditions that
were previously used and combined with additional experiments
which have not been tried before but was within the limits tested
previously (Table 12). In addition water samples of different char-
acteristics from other natural NOM sources such as Bekok Dam
water and Ulu Pontian river were also employed in the verica-
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210 207

Fig. 16. Interaction graph (a and b) and contour plot (c) of membrane permeability from the model equation: effect of pH and alum dose.

tion process. The detailed characteristic of the Bekok Dam water ual and percentage error analysis. The percentage error between
and Ulu Pontian river are given elsewhere by Zularisam et al. [22]. actual and predicted value of both responses over a selected
The obtained actual values and its associated predicted values range of operating levels are calculated based on Eqs. (13) and
from the selected experiments were compared for further resid- (14).

Table 12
Results of operating conditions with experimental design in conrmation runs.

Run factor NOM removal (%) Permeability (LMHBar)

x1 (pH) x2 (SUVA) x3 (Alum) Actual Predicted Residual Error (%) Actual Predicted Residual Error (%)

5 3.3 3.0 80.58 83.52 2.94 3.64 31.24 29.77 +1.47 4.71
5 3.3 1.8 53.50 55.78 2.28 4.26 14.78 14.33 +0.45 3.04
5 1.27 3.6 55.48 52.65 +1.83 3.36 20.17 19.33 +0.84 4.16
5 4.31 1.8 70.24 67.77 +2.47 3.52 25.27 24.09 +1.18 4.65
7.5 1.27 3.6 60.68 63.70 3.02 4.97 16.86 16.14 +0.72 4.27
7.0a 1.29 3.0 60.84 57.86 +2.98 4.89 25.09 23.88 +1.21 4.82
7.14b 2.39 3.0 71.60 68.24 +3.36 4.68 29.75 28.52 +1.23 4.13
a
Ulu Pontian river.
b
Bekok Dam water.
208 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210

Table 13
Results of optimum operational conditions for Yong Peng river.

Proposed optimal conditions Predicted removal (%DOC) Predicted permeability (LMHBar) Conrmation runs

Actual removal (%DOC) Actual permeability (LMHBar)

pH 5.48
79.50 31.29
SUVA 3.24 81.28 30.61
(2.24%) (2.17%)
Alum 3.00

Number in parenthesis means percentage of error.

Residual = (Actual value Predicted value)
Residual
% Error = 100%
Actual value
Results of Table 12 have shown that the percentage errors are
ranging from 3.36% to 4.97% and 3.04% to 4.71% for NOM removal
and membrane permeability, respectively. Thus implied that the
empirical model developed were considerably accurate for both
responding terms (NOM removal and membrane permeability) as
the percentage error between the actual and predicted values were
well within the value of 5%, suggesting that the model adequacy is
(13) reasonably within the 95% of prediction interval. By this means fur-
ther analysis with regards to ideal operational process for optimal
(14) membrane performance would be based on this developed model.
3.2.2. Process optimization
Considering the previous discussion, main effect of alum dose,
pH and SUVA were found more dominant than their interaction
effects with respect to both NOM removal and membrane perme-
ability. Nevertheless one cannot simply neglect the importance of
various interaction effects, for that interaction among them had
only little inuence on responses because any individual factor that
involved in interactions have to be considered jointly. In general
for any given separation, there is usually a trade-off relationship of
between removal and permeability, where both parameters tend
to exhibit a contradictory relation, that an increase in removal
through a single effort was often accompanied with a decrease in
permeability, or vice versa. In conjunction, this phenomenon was
in a good accordance with results of Run 11 and Run 19 (Table 7)
which demonstrated dramatically low membrane permeability
(8.7 LMHBar and 8.66 LMHBar) were corresponded with high NOM
removal efciency (66.3% and 75.8%). Hence a desirable combina-
tion of pH, SUVA and alum dose is required in order to achieve
the optimum operational conditions for NOM removal and mem-
brane permeability. Utilizing the optimization mode capability of
the software enables the prediction of response complete with 95%
prediction interval. Optimization procedure has been conducted
for the nom source waters of Yong Peng and the prediction results
of the empirical model are tabulated in Table 13. The concentration
level of pH and alum dose were set to range within the levels dened
previously while SUVA of NOM source water was xed to its natural
value. Results have shown optimum pH, SUVA and alum dose for
optimal NOM removal and membrane permeability of Yong Peng
water were determined to be 5.48, 3.24 L mg1 m1 and 3.0 mg Al/L,
respectively. Under these proposed optimized conditions, the max-
imum value of removal and permeability predicted from the model
were 81.28% and 30.61 LMHBar. In order to conrm the predicted
optimization conditions, experimental conrmation runs were per-
formed by employing the suggested model conditions. Apparently
the optimal values of 79.50% and 31.29 LMHBar were obtained,
respectively. It is worth to note results of the experimental car-
ried out here adequately implied that the proposed mathematical
models suggested are reasonably accurate and reliable as most of
the actual values for the conrmation runs are well within the 95%
prediction interval, hence it could reliably be employed for the pre-
diction of optimum coagulationUF membrane process conditions
with respect to optimal production of high quality potable drinking
water.

4. Conclusions

A Full factorial design and central composite design (CCD) of

Response surface methodology (RSM) can be used to determine
the signicant variables and optimum condition for hybrid pro-
Fig. 17. Conceptual model postulating the effect of coagulation condition on organic cess of coagulationUF membrane with respect to NOM removal
removal and membrane permeability during coagulationUF membrane ltration. and membrane permeability. Experimental results show that a UF
 A.W. Zularisam et al. / Separation and Purication Technology 65 (2009) 193210
process with coagulation pretreatment has a great potential for
drinking water treatment. This innovative technology has been
found to signicantly dependent on addition of coagulant, suit-
able pH and with condition of sufcient SUVA of NOM source,
in the perspective to promote greater colloidal destabilization,
charge neutralization and agglomeration of dissolved organic mat-
ter (micro-ocs). The effectiveness of coagulation pretreatment and
followed by a direct UF with respect to NOM removal and mem-
brane permeability appears to be a result of complex interactions
between membrane surface and NOM occulant characteristics.
As a matter of fact these interactions may pronouncedly differ
depending on the pH adjustment, coagulant dosing and NOM frac-
tions of the particulate water (relative distribution of hydrophilic
and hydrophobic NOM composition). Although proper adjustment
of pH and optimal coagulant dosage is considered promising in
reducing membrane fouling and providing permeate quality far
beyond the current regulatory, the relative NOM composition (HPI
versus HPO fractions) is also critically important with respect
to minimization of membrane fouling and improving permeate
quality as it could inuence the coagulated ocs morphological
characteristics, through selective domination of either charge neu-
tralization or sweep coagulation mechanisms. Furthermore this
treatment system also demonstrates reduction in the occula-
tion hydraulic retention as the required ocs need only be larger
(pin-sized ocs) than the membrane pore size. This represents a
benet of requiring lesser coagulant consumption than would be
required for the formation of settleable ocs, improve production
capacity due to sedimentation process elimination, eliminating
ocs settleability concerns, smaller footprint and lower operating
costs associating to minimal coagulant dosage, sludge produc-
tion and treatment duration. It should also be pointed out that
selection of optimal pH with respect to maximum NOM removal
depends greatly on the relative concentration of NOM composition.
Apparently charge neutralization coagulation is preferable for NOM
source predominated with humic/hydrophobic fraction (Yong Peng
water), owing to the charge interaction, whereas sweep coagulation
mechanism through surface adsorption is more favorable for NOM
source primarily occupied by less negatively charged of non-humic
compounds. In conjunction possession of moderately high SUVA
property in NOM source is preferable as it could essentially inu-
enced the possibility of charge neutralization mechanism, instead
of surface adsorption and sweep coagulation, which was noticeably
responsible in changing the ocs morphological characteristic (big-
ger pin-sized ocs), lower FRT requirement, greater NOM removal
as well as lower ux decline. Therefore in future applications, NOM
composition should be critically considered in respect to optimal
selection of coagulation pH zone and the suitability of alum dosage
to be applied.
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