Environ. Sci. Technol.
2000, 34, 3710-3716
Relating Nanofiltration Membrane
Performance to Membrane Charge
(Electrokinetic) Characteristics
A M Y E . C H I L D R E S S * , A N D
MENACHEM ELIMELECH
Department of Civil Engineering, Mail Stop 258,
University of Nevada, Reno, Nevada 89557-0152, and
Department of Chemical Engineering, Environmental
Engineering Program, P.O. Box 208286, Yale University,
New Haven, Connecticut 06520-8286
The performance (i.e., water flux and solute rejection) of
a thin-film composite aromatic polyamide nanofiltration
membrane and its relation to membrane surface charge
(electrokinetic) characteristics were investigated. Membrane
performance and streaming potential measurements
were carried out as a function of pH for several solution
chemistries, including an indifferent electrolyte, humic acid,
and anionic and cationic surfactants. Performance
results for the membrane were interpreted by relating the
water flux and salt/ion rejection to the membrane charge
characteristics. In the case of the indifferent electrolyte (NaCl),
water flux and salt passage were maximal at the membrane
pore isoelectric point (pH 5) primarily due to decreased
electrostatic repulsion and increased pore volume (size) in
the cross-linked polymer network. Ion rejection is directly
related to the membrane pore charge and is attributed
to co-ion electrostatic repulsion (exclusion). At low pH,
negative rejection of protons was observed, demonstrating
the classical behavior of a more mobile co-ion in a
mixture of electrolytes (NaCl and HCl). Suwannee River
humic acid was found to have very little effect on the short-
term performance of the membrane, despite its significant
influence on membrane -potential. Sodium dodecyl
sulfate, on the other hand, had significant effects on the
water flux and salt rejection. Association of the surfactant
molecules (i.e., hemimicelle formation) at the membrane-
solution interface was analyzed in terms of membrane
charge characteristics. It is proposed that the adsorbed
surfactant molecules in the form of hemimicelles or a bilayer
provide an additional filtration layer that results in
reduced water flux and increased salt rejection.
Introduction
Nanofiltration (NF) membranes are used in a wide range of
drinking water, wastewater, and industrial applications (1-
4). Separation by nanofiltration membranes occurs primarily
due to size exclusion and electrostatic interactions (1, 5-8).
For uncharged molecules, sieving or size exclusion is most
responsible for separation; for ionic species, both sieving
and electrostatic interactions are responsible for separation
* Corresponding author phone: (775)784-6942; fax: (775)784-1390;
e-mail: amyec@unr.edu.
University of Nevada.
Yale University.
3710 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 17, 2000
(7-9). For all applications, membrane surface and pore
charge characteristics play a significant role in the transport
of water and solute molecules through the membrane.
Additionally, the interaction of colloids and charged mac-
romolecules with the membrane and subsequent fouling of
the membrane are dependent on the surface and pore charge
properties (10).
Previous experimental studies on nanofiltration mem-
branes have investigated to some extent the role of surface
and pore charge characteristics on the performance of
nanofiltration membranes [e.g., Nystrom et al. (1), Bowen et
al. (11), Braghetta et al. (12), Hong and Elimelech (13),
Pontalier et al. (14), Blank et al. (15), Peeters et al. (8)].
However, these investigations did not systematically study
membrane performance as a function of solution pH.
Studying water flux and solute rejection as a function of pH
is mandatory because as pH changes so do several of the
system characteristics. The charge and resulting -potential
of the membrane depend on the pH of the system because
membrane functional groups protonate and deprotonate over
the pH range. The charge of the membrane is significant to
membrane performance because charge affects the elec-
trostatic repulsion between the ions or charged molecules
and the membrane surface. Additionally, because of dis-
sociation of membrane functional groups, the pH of the
system may affect the openness of the membrane. This
affects the size exclusion mechanism of removal for nano-
filtration membranes. Last, pH may affect the characteristics
of the molecules in the test solution. For example, at low pH,
humic functional groups will protonate, and at high pH, they
will deprotonate. This, in turn, will play a role in the
interaction between the humic molecules and the membrane.
A thorough understanding of the interrelation between
membrane performance and membrane chemical charac-
teristics is of paramount importance in membrane research.
The objective of this paper is to systematically investigate
the performance (i.e., water flux and solute rejection) of a
thin-film composite aromatic polyamide nanofiltration
membrane under a wide range of solution chemistries and
to relate the performance of the membrane to its chemical
and charge characteristics. Both the performance and the
charge properties are evaluated at the various solution
chemistries as a function of pH. A mechanistic explanation
for the water flux and salt/ion rejection behaviors at the
various solution chemistries is provided.
Materials and Methods
Representative NF Membrane. The representative NF mem-
brane used in this investigation was the NF-55 membrane
(FilmTec Corp., Minneapolis, MN). It is a fully aromatic thin-
film composite membrane. According to the manufacturer,
it has an operational pH range of 3-9 and a maximum
operating temperature of 35 C. The recommended operating
pressure is approximately 70 psi (483 kPa). The membrane
was received as a wet flat sheet and was stored in deionized
water (NanoPure II, Dubuque, IA) at 5 C.
Solution Chemistries. Certified ACS grade sodium chlo-
ride (Fisher Scientific, Pittsburgh, PA) was used for the
background inorganic electrolyte solution. Certified grade
hydrochloric acid and sodium hydroxide (Fisher Scientific,
Pittsburgh, PA) were used for pH adjustments.
Suwannee River humic acid standard (SRHA) was received
in a freeze-dried form from the International Humic Sub-
stances Society (Golden, CO). The humic acid solution was
made by dissolving the freeze-dried powder in deionized
10.1021/es0008620 CCC: $19.00 2000 American Chemical Society
Published on Web 07/26/2000
water and adjusting the pH to 8.2. The molecular weight of
the SRHA is between 3000 and 5000 (16), and the major
functional groups are carboxylic (4.1 mequiv/g) and phenolic
(2.1 mequiv/g) (17).
Certified grade sodium dodecyl sulfate (SDS) (Fisher
Scientific, Pittsburgh, PA) and dodecyl trimethylammonium
bromide (DTAB) (Aldrich Chemicals, Milwaukee, WI) were
used as model anionic and cationic surfactants, respectively.
The surfactant concentration used in the experiments was
1 mM. This concentration is below the corresponding critical
micelle concentrations of approximately 3.2 and 7.9 mM (in
the presence of 0.01 M NaCl) for SDS and DTAB, respectively
(18).
Streaming Potential Measurements. Streaming potential
measurements were performed with the BI-EKA (Brookhaven
Instruments Corp., Holtsville, NY). This instrument utilizes
silver/silver chloride electrodes to measure the streaming
potential that is induced when an electrolyte solution flows
across a stationary, charged membrane. -potential is
calculated from the measured streaming potential using the
Helmholtz-Smoluchowski equation (19, 20) with the Fair-
brother and Mastin substitution (21). A detailed description
of the instrument, measurement procedure, and -potential
calculation can be found elsewhere (22, 23).
The streaming potential of the NF-55 membrane was
evaluated over the pH range of 3-9 for each solution
chemistry. The results shown for each pH value are an average
of six measurements taken at that pH. Measurements were
performed at room temperature (approximately 23 C).
Membrane Performance Measurements. The perfor-
mance (water flux and solute rejection) of the NF-55
membrane under the various solution chemistries was
evaluated using a closed-loop bench-scale membrane test
unit. In this unit, the test solution is pumped from a solution
reservoir, through two membrane cells (in parallel), and back
to the reservoir. The pump (Hydra-Cell, Wanner Engineering,
Inc., Minneapolis, MN) is capable of providing pressures up
to 1000 psig (6900 kPa) and flow rates up to 4.2 L/min. The
solution reservoir sits on a magnetic stirrer and houses a
stainless steel cooling coil that is connected to a refrigerated
recirculating chiller (Fisher Scientific, Pittsburgh, PA). The
temperature of the system is monitored with a thermometer
and is kept constant at 20 C. The membrane cells have an
active area of 3.2 by 8.2 cm and operate in cross-flow mode;
both the permeate and concentrate are recycled. The
operating pressure [either 60 or 80 psi (414 or 552 kPa)
depending on the solution chemistry] is controlled by a back-
pressure regulator and monitored with a pressure gauge.
The flow rate across each membrane cell (1.9 L/min
corresponding to a cross-flow velocity of 33 cm/s) is also
monitored during the entire run.
The membranes for each run are taken from storage and
rinsed in flow-through mode with 15 L of deionized water.
They are then placed into the membrane cells and given 45
h to stabilize with 0.01 M NaCl. For the humic acid and
surfactant runs, the humic acid or surfactant is added
immediately after the stabilization period. Prior to making
any measurements, there are two 30-min equilibration
periods during which the water flux is monitored. If the water
flux is constant over these equilibration periods, the mem-
brane performance measurements are started. Performance
is first evaluated at ambient pH (pH 5.7). The solution is
then adjusted to pH 9 by the addition of NaOH. From pH 9,
the pH is incrementally dropped to pH 3 by additions of HCl,
and performance is evaluated at each pH increment after a
10-min equilibration period. After pH 3, the pH is raised
back to pH 5.7, and the performance is evaluated there to
ensure that fouling has not occurred and that the initial water
flux and salt rejection are maintained.
FIGURE 1. Comparison of -potential of NF-55 membrane in the
presence of an indifferent electrolyte (NaCl), Suwannee River humic
acid (SRHA), and sodium dodecyl sulfate (SDS). The SRHA and SDS
experiments were carried out with a background electrolyte of 0.01
M NaCl.
Sample Analyses. Solution pH was monitored with a pH
meter (Accumet model 15, Fisher Scientific, Pittsburgh, PA),
and total ion rejection was measured with a conductance
meter (YSI Co., Inc., Yellow Springs, OH). Sodium and chloride
ion selective electrodes (ISE models 86-11BM and 96-127BN,
respectively, Orion, Boston, MA) were used to determine
individual ion rejection. For each electrode, a calibration
curve was developed using three serial dilutions. The three
standards (0.1, 1, and 10 mM) were selected to bracket the
concentrations of the feed and permeate solutions. The
appropriate amount of ionic strength adjuster (Orion Re-
search Inc., Boston, MA) was added to each sample prior to
measurement.
Results and Discussion
Membrane -potential in the Presence of Indifferent
Electrolyte. In the presence of an indifferent electrolyte (0.01
M NaCl), the NF-55 membrane has a slightly positive
-potential at the lowest pH (pH 3), passes through an
isoelectric point at approximately pH 3.2, and is negatively
charged above pH 3.2 (Figure 1). -potential curves of this
shape are characteristic of amphoteric surfaces, or surfaces
with both acidic and basic functional groups.
Because fully aromatic thin-film composite membranes
are made by the interfacial polymerization reaction of 1,3-
benzenediamine with trimesoyl chloride, carboxyl and amine
functional groups would be expected on the membrane
surface (22-26). The positive surface charge below the
isoelectric point would result from the protonation of the
amine functional groups (tNH2 f tNH3+), and the negative
charge above the isoelectric point would result from depro-
tonation of the carboxyl groups (tCOOH f tCOO-). A
detailed description of the mechanisms controlling the
surface charge of various thin-film composite RO and NF
membranes was presented in an earlier publication (23).
Membrane -potential in the Presence of Humic Acid.
The most obvious effect of SRHA on the -potential of the
NF-55 membrane (Figure 1) is that it causes the membrane
to be more negatively charged over the entire pH range. This
indicates that the humic macromolecules readily adsorb to
the membrane surface and that the negatively charged
VOL. 34, NO. 17, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3711
 FIGURE 3. Schematic of adsorption of sodium dodecyl sulfate (SDS)
molecules onto the membrane surface.

FIGURE 2. Comparison of -potential of NF-55 membrane in the

presence of sodium dodecyl sulfate (SDS) at two pH conditions.
The experiments were carried out with a background electrolyte
of 0.01 M NaCl.

functional groups of the humics dominate the membrane

surface charge. In the presence of SRHA, the NF-55 mem-
brane displays no isoelectric point over the pH range
investigated. At low pH, where the membrane and SRHA are
oppositely charged, adsorption of SRHA is favorable because
of both electrostatic and hydrophobic interactions. At higher
pH values, where the SRHA and the membrane are similarly
charged, adsorption is likely dominated by hydrophobic
interactions. Discussion on the effect of SRHA on the
-potential of other NF (and RO) membranes can be found
elsewhere (23, 27).
Membrane -potential in the Presence of Surfactants.
The effect of SDS on the -potential of the NF-55 membrane
is somewhat similar to the effect of SRHA in that the negatively
charged sulfate functional groups of the surfactant molecules
cause the membrane to become more negatively charged
(Figure 1). The adsorption characteristics of surfactants are
governed by the molecular structure of the surfactant
molecules (e.g., type of polar head, structure and length of
hydrocarbon chain) and the characteristics of the membrane
surface (e.g., charge, hydrophobicity) (28-30). As the solution
pH changes, the dominant mechanism of adsorption also
changes. At high pH, hydrophobic interactions between the
SDS molecules and the negatively charged membrane surface
result in significant SDS adsorption and a more negative
membrane -potential. At low pH, electrostatic attraction
and possible surfactant association (i.e., hemimicelle forma-
tion) at the membrane surface have an even greater effect
on -potential. This is best demonstrated in Figure 2 where
the higher concentrations of SDS have a much more dramatic
effect on -potential at pH 3 as compared to pH 8.
Hemimicelle formation was initially proposed by Gaudin
and Fuerstenau (31). Hemimicelles result from the surfactant
ions associating with each other to remove their hydrocarbon
chains from the bulk water and, hence, to reduce the free
energy of the system (32). Hemimicelles, or two-dimensional
surfactant aggregates, form at the solid-solution interface
when the hemimicelle concentration (HMC) of the system
has been exceeded. The HMC is the point at which there is
a sharp increase in adsorption which reflects the transition
from individual surfactant ion adsorption to surfactant
association at the surface (32-34). In a study of SDS
FIGURE 4. Comparison of -potential of NF-55 membrane in the
presence of dodecyl trimethylammonium bromide (DTAB) at two
pH conditions. The experiments were carried out with a background
electrolyte of 0.01 M NaCl.
adsorption onto alumina, the HMC was found to occur at
approximately 0.06 mM (33).
The differences in SDS adsorption at low pH and high pH
(Figure 2) are shown schematically in Figure 3. At pH 3, the
membrane initially has a slight positive charge (Figure 1),
and adsorption occurs due to electrostatic attraction between
the negatively charged polar head of the surfactant ions and
the charged membrane surface (Figure 3). As their concen-
tration increases, the surfactant ions begin associating with
each other and form surfactant aggregates (or hemimicelles).
From Figure 2, the HMC appears to occur around 0.01 mM
SDSsat this concentration there is a dramatic change in the
slope of the -potential curve representing transition from
individual ion adsorption to surfactant association. At pH 8,
the membrane initially has a negative charge (Figure 1), and
adsorption occurs due to hydrophobic interactions between
the surfactant tail and the membrane surface (Figure 3). As
the surfactant concentration increases, the membrane
becomes slightly more negative (Figure 2) due to a larger
number of adsorbed surfactant molecules (Figure 3).
Figures 4 and 5 show the adsorption of DTAB, a cationic
surfactant, at two pH values. At pH 3, when the membrane
is initially positively charged (Figure 1), adsorption is due to
hydrophobic interactions (Figure 5). Adsorption increases

3712 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 17, 2000
FIGURE 5. Schematic of adsorption of dodecyl trimethylammonium
bromide (DTAB) molecules onto the membrane surface.
with increasing DTAB concentration, and the membrane
becomes more positively charged. At pH 8, the membrane
is initially negatively charged (Figure 1), and adsorption
occurs due to electrostatic attraction (Figure 5). Hemimicelle
formation (Figure 5) may start to occur at the highest
concentration shown in Figure 4 (0.1 mM DTAB).
Membrane Performance in the Presence of Electrolyte
Solution. The NF-55 is a loose nanofiltration membrane.
It is one of several NF membranes that is believed to have
the same polymeric structure as the FT-30 membrane
(FilmTec Corp., Minneapolis, MN) but has been post-treated
with phosphoric acid and tannic acid to open up the pores
(26). Other membranes in this category include the NF-40,
NF-70, and NF-90 (FilmTec Corp., Minneapolis, MN).
Nystrom et al. (1) performed pore streaming potential
measurements on the NF-40 and found the pores to have a
-potential curve similar to the -potential curve of the NF-
55 membrane surface (measured in the current investigation)
with two exceptions. First, the magnitude of the positive and
negative pore -potential is less than it is for the NF-55
membrane surface. Second, and more important, the iso-
electric point of the NF-40 membrane pores is approximately
at pH 5. By comparing the NF-40 membrane pore isoelectric
point [from Nystrom et al. (1)] with observations of water
flux and electrolyte rejection for the NF-55 membrane in the
current investigation (Figure 6), it appears that the charge
of the membrane pores may have a significant effect on
membrane flux and rejection. Because pore -potential
measurements were not conducted in the current investiga-
tion, this could not be verified. However, it would be expected
that pore streaming potential measurements are as impor-
tant, if not more important, than surface streaming potential
measurements in controlling water flux and salt rejection
because the NF-55 is a loose, porous NF membrane.
(a) Water Flux. The flux of the NF-55 membrane (Figure
6a) is relatively constant over the entire pH range with the
exception of a slight peak at pH 5 where it is expected that
the NF-55 membrane pores are uncharged. The peak in flux
(and corresponding dip in rejection shown in Figure 6b) may
be caused by several mechanisms including (i) increased
pore size due to conformational changes of the cross-linked
membrane polymer structure, (ii) increased apparent water
permeability due to decreased electroviscous effect, and (iii)
increased net driving pressure due to decreased osmotic
pressure at the membrane surface. The potential effect of
each of these mechanisms on the NF-55 membrane is
discussed below.
The lack of electric surface charge in the pores may cause
the membrane to be looser than when the pores are
charged. In a study of UF membranes with carboxylic acid
groups (35), evidence was presented that carboxylic acid
segmental conformation is responsible for the pH-sensitive
molecular sieve effect of copolymer membranes. The pore
FIGURE 6. Flux (a) and conductivity rejection (b) of NF-55 membrane
as a function of pH. Experiments were carried out with 0.01 M NaCl
at a pressure of 414 kPa, a cross-flow velocity of 33 cm/s, and a
temperature of 20 C.
size of the membrane was found to be significantly reduced
at higher pH values because the charged tCOO- groups
adopt an extended chain conformation due to electrostatic
repulsion between them. This expanded conformation
reduces the pore size (or pore volume) of the membrane and
thereby causes decreased flux and increased salt rejection.
The pore size of the membrane changes with pH because
the cross-linked polymer network will either shrink or expand
(36).
Extending this explanation to the NF-55 membrane, which
has both carboxyl and amine functional groups, the pore
size of the membrane would be reduced at both high and
low pH. At high pH, the carboxyl groups would be depro-
tonated (tCOO-), and at low pH, the amino groups would
be protonated (tNH3+). In both cases, the electrostatic
repulsion between the charged groups would cause a
reduction in pore size. However, at the pore isoelectric point,
the pore size would not be reduced, and therefore, water flux
would be at a maximum and salt rejection would be at a
minimum. The experimental results in Figure 6 confirm this
proposed mechanism. From pH 3 to pH 5, where the pores
are gradually expanding as they are becoming less positively
charged, the water flux increases. At pH 5, the water flux
peaks, and salt rejection reaches a local minimum. From pH
5 to pH 8, where the pores are gradually shrinking as they
are becoming more negatively charged, the water flux
declines. Above pH 8, the -potential of the pores begins to
level off and so does the water flux.
The electroviscous effect is a physical phenomenon that
occurs when an electrolyte solution is pressed through a
narrow capillary or pore with charged surfaces (37). This
effect refers to the back-flow of counterions and water in the
VOL. 34, NO. 17, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3713

FIGURE 7. Individual ion rejection (a) and proton rejection (b) of
NF-55 membrane as a function of pH. Experiments were carried out
with 0.01 M NaCl at a pressure of 414 kPa, a cross-flow velocity
of 33 cm/s, and a temperature of 20 C.
double layer adjacent to the capillary pore surface due to a
streaming potential that develops between the capillary ends.
The electroviscous effect is least pronounced at the pore
surface point of zero charge (or isoelectric point) where
double-layer effects are negligible. At low pore surface charge,
the permeating solution appears to exhibit a reduced viscosity
when its flow rate is compared with the flow at high pore
surface charge. Accordingly, flux would be at a maximum
when the capillary is uncharged, or in other words, at the
membrane pore isoelectric point. This phenomenon has been
shown previously for ceramic (38-41) and polymeric mem-
branes (40) and may contribute to the flux maximum shown
in Figure 6a for the NF-55 membrane.
Changes in osmotic pressure at the membrane surface
may also be used to explain the flux curve in Figure 6a. As
the pH increases from pH 5 to pH 9, the salt rejection increases
(Figure 6b). Increased salt rejection, coupled with concen-
tration polarization, results in increased osmotic pressure.
Because the operating pressure of the system was kept
constant, the increased osmotic pressure results in a
decreased net driving pressure which, in turn, leads to
decreased water flux.
(b) Salt, Individual Ion, and Total Molar Rejection. The
salt rejection (Figure 6b) increases as pH increases with the
exception of the dip at pH 5. Rejection of loose nanofiltration
membranes is due to both size exclusion and co-ion
electrostatic repulsion (or charge exclusion). Generally, when
dealing with loose NF membranes, size exclusion is more
important in understanding the rejection of uncharged solute
molecules, and electrostatic repulsion is more important for
the rejection of ionic species.
3714 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 17, 2000
FIGURE 8. Total molar rejection (combined rejection of [H+], [Na+],
and [Cl-]) of NF-55 membrane as a function of pH. Experiments
were carried out with 0.01 M NaCl at a pressure of 414 kPa, a
cross-flow velocity of 33 cm/s, and a temperature of 20 C.
TABLE 1. Ion Characteristics
ionic mobility hydrated molar conductance
ion (10-8 m2 V-1 s-1) radius (nm) (10-3 m2 mol-1 -1)
H+ 36.3 0.28 35.0
OH- 20.5 0.30 19.8
Na+ 5.19 0.36 5.01
Cl- 7.91 0.33 7.63
In Figure 6b, the decrease in salt rejection from pH 9 to
pH 5 is attributed to decreasing co-ion charge exclusion (1,
3, 26). At pH 9, where the membrane pore is more negatively
charged, the chloride ion (the co-ion) experiences electro-
static repulsion from the membrane pore and will be rejected
by the membrane (Figure 7a). Because electroneutrality of
the permeate solution must be maintained, the Na+ will also
be rejected (Figure 7a). (At pH 9, the proton and hydroxide
ion concentrations, 10-9 M and 10-5 M, respectively, are
negligible.) As the pH decreases, so does the electrostatic
repulsion and therefore ion rejection. At pH 5, the rejection
reaches a local minimum, as the lack of charge leads not
only to no electrostatic repulsion but also to increased pore
size and salt passage. From pH 4 to pH 3, where the
membrane pores are positively charged, the sodium ion (the
co-ion) will be rejected by the membrane, and because of
electroneutrality, the chloride ion will also be rejected (Figure
7a). However, from pH 4 to pH 3, salt rejection (Figure 6b)
decreases dramatically because of extensive proton (H+)
passage through the membrane (Figure 7b), as discussed in
the next subsection.
When the graph of conductivity rejection as a function of
pH (Figure 6b) is compared to a graph of total molar rejection
(the total number of moles of all ions that are rejected) as
a function of pH (Figure 8), one major difference is apparent.
In the plot of salt rejection (Figure 6b), the minimum at pH
5 is shown to be a local minimum. On the other hand, in the
plot of total molar rejection (Figure 8), the minimum at pH
5 is shown to be a global minimum. The high molar
conductance (35 10-3 m2/mol-) (Table 1) of the protons
in the permeate contribute much more significantly to the
permeate conductivity than that of sodium ions (5.0 10-3
m2/mol-) or chloride ions (7.6 10-3 m2/mol-). The plot
of total molar rejection (Figure 8) takes into account only the
concentration of ions, not their molar conductance and,
therefore, shows the rejection to improve as the pH decreases
from 5 to 3.
(d) Negative Rejection of Protons. Negative rejection of
protons is shown in Figure 7b. When the pH of the feed
FIGURE 9. Effect of Suwannee River humic acid (SRHA) on the
water flux (a) and conductivity rejection (b) of NF-55 membrane as
a function of pH. Experiments were carried out at a pressure of 414
kPa, a cross-flow velocity of 33 cm/s, a temperature of 20 C, and
with a background electrolyte of 0.01 M NaCl.
solution is 3.0, the pH of the permeate solution is 2.7; this
indicates that negative rejection occurs due to significant
proton passage through the membrane. Negative rejection
of protons occurs when the concentration of protons in the
permeate (10-2.7 M) is greater than the concentration of
protons in the feed (10-3 M); it does not imply that protons
are created, just that the small volume of permeate has
proportionately more protons than the much larger volume
of feed. Negative rejection of protons at pH 3 demonstrates
the classical behavior of a more mobile co-ion in a mixture
of electrolytes. The electrolytes are HCl and NaCl; the co-
ions at pH 3, where the membrane pores are positively
charged, are H+ and Na+. Because protons have a higher
ionic mobility and are smaller than sodium ions (Table 1),
proton rejection is made worse by the presence of the less
permeable sodium ions (8). Furthermore, at pH 3, the molar
ratio of protons to sodium ions is 0.1. When the ratio of the
more permeable ion to the less permeable ion is low, negative
rejection of the more permeable ion is possible (8). Note that
due to the higher passage of protons, more chloride ions will
transport through the membrane to maintain electroneu-
trality in the permeate as shown in Figure 7a. Numerous
investigators have encountered negative rejection, both
experimentally [e.g., Hoffer and Kedem (42), Lonsdale et al.
(43), Akred et al. (44), Vonk and Smit (45), Tsuru et al. (46)]
and theoretically [e.g., Hoffer and Kedem (42), Dresner (47),
Lonsdale et al. (43), Akred et al. (44), Tsuru et al. (46), Nielsen
and Jonsson (48), Hagmeyer and Gimbel (3)].
Membrane Performance in the Presence of Humic Acid.
The water flux and total ion rejection of the NF-55 membrane
FIGURE 10. Effect of sodium dodecyl sulfate (SDS) on the water
flux (a) and conductivity rejection (b) of NF-55 membrane as a
function of pH. Experiments in the presence of SDS were carried
out at a pressure of 552 kPa, a cross-flow velocity of 33 cm/s, a
temperature of 20 C, and with a background electrolyte of 0.01 M
NaCl. Experiments in the absence of SDS were carried out at a
pressure of 414 kPa, a cross-flow velocity of 33 cm/s, a temperature
of 20 C, and with a background electrolyte of 0.01 M NaCl.
does not change significantly in the presence of SRHA (Figure
9). Therefore, the presence of humics is not believed to
significantly affect the short-term performance of the mem-
brane. In a recent study of the effect of humic fouling layers
on membrane performance (49), salt rejection was found to
improve in the presence of organic fouling layers. In the
current investigation, flux was found to decrease just slightly
in the presence of SRHA.
Several steps were taken to ensure that the observed effects
of SRHA on the membrane performance characteristics were
due to membrane surface modification rather than mem-
brane fouling. After adding the SRHA to the solution reservoir,
the humic acid was given a short time to equilibrate with the
membrane surface. After the equilibration, a measurement
of flux was taken to serve as the baseline flux. Then, after 30
min, a second measurement of flux was taken and checked
to make sure that flux had not decreased over the 30-min
period. Finally, after another 30-min equilibration period
and another flux measurement to ensure that the flux still
had not changed, the actual salt rejection and water flux
measurements were taken. The second way of verifying that
the effects of the humic on the membrane was only due to
short-term surface modification was to compare performance
characteristics initially (at ambient pH) with performance
characteristics at the end of the experiments (when the pH
is returned to approximately ambient pH) to make sure the
membrane had not fouled through the duration of the
VOL. 34, NO. 17, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3715
experiment. In this manner, it is assured that any changes
in performance at different pH values are due to surface
modification of the membrane at that pH.
Membrane Performance in the Presence of Surfactants.
Unlike the SRHA, the SDS had significant effects on the flux
and rejection of the NF-55 membrane (Figure 10). Advective
transport of the SDS may result in a secondary filtration layer
of SDS molecules on the membrane surface and cause
decreased flux and increased rejection of the mem-
brane. Additionally, the anionic surfactant alters the charge
and hydrophobicity of the membrane. Because of signifi-
cant flux loss through the membrane, the operating pres-
sure of the NF-55 membrane was immediately increased
from 60 to 80 psi (414-552 kPa) upon addition of SDS to the
system. This contributes to the increased flux at high pH
(Figure 10a).
The effect of the anionic surfactant is most apparent at
low pH because at low pH the SDS molecules will associate
and form hemimicelles as discussed earlier. When the
negatively charged headgroups of the surfactant molecules
are aligned toward the membrane surface, the hydrocarbon
chains of the surfactant will be dangling in the bulk solution.
Because this is not a thermodynamically favorable formation
for the hydrocarbon chains, the hydrocarbon chains of the
surfactant ions on the surface will associate with the
hydrocarbon chains of the surfactant ions in the bulk solution
to form hemimicelles or a bilayer of SDS molecules (32). The
result is substantially decreased water flux and increased
salt rejection (Figure 10). This situation would not be as likely
to occur at high pH because the membrane is negatively
charged, and the hydrocarbon chains will be attracted to the
membrane surface leading to adsorption of individual
molecules (23). Therefore, only a minimal effect of the
surfactant ions is observed at high pH (Figure 10).
Acknowledgments
This research was supported in part by the U.S. Bureau of
Reclamation, Water Treatment and Engineering Research
Group. The findings reported in this paper do not necessarily
reflect the views of this agency, and no official endorsement
should be inferred. We would also like to acknowledge Shivaji
Deshmukh for his contribution to the streaming potential
and fouling experiments.
Literature Cited
(1) Nystrom, M.; Kaipia, L.; Luque, S. J. Membr. Sci. 1995, 98, 249-
262.
(2) Archer, A. C.; Mendes, A. M.; Boaventura, R. A. R. Environ. Sci.
Technol. 1999, 33, 2758-2764.
(3) Hagmeyer, G.; Gimbel R. Sep. Purif. Technol. 1999, 15, 19-30.
(4) Xu, Y.; Lebrun, R. E. Desalination 1999, 122, 95-106.
(5) Eriksson, P. Environ. Prog. 1988, 7, 58-62.
(6) Yaroschuck, A.; Staude, E. Desalination 1992, 86, 115-134.
(7) Garba, Y.; Taha, S.; Gondrexon, N.; Dorange, G. J. Membr. Sci.
1999, 160, 187-200.
(8) Peeters, J. M. M.; Mulder, M. H. V.; Strathmann, H. Colloids
Surf. A 1999, 150, 247-259.
(9) Tsuru, T.; Wang, X. L.; Nakao, S. I.; Kimura, S. J. Chem. Eng. Jpn.
1995, 28, 372-382.
(10) Wiesner, M. R.; Chellam, S. Environ. Sci. Technol. 1999, 33, 360-
366.
(11) Bowen, W. R.; Mohammad, A. W.; Hilal, N. J. Membr. Sci. 1997,
126, 91-105.
(12) Braghetta, A.; DiGiano, F. A.; Ball, W. P. J. Environ. Eng. 1997,
123, 628-641.
(13) Hong, S.; Elimelech, M. J. Membr. Sci. 1997, 132, 159-181.
(14) Pontalier, P.-Y.; Ismail, A.; Ghoul, M. Sep. Purif. Technol. 1997,
12, 175-181.
(15) Blank, R.; Muth, K.-H.; Proske-Gerhards, S.; Staude, E. Colloids
Surf. A 1998, 140, 3-11.
3716 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 17, 2000
(16) Liang, L.; Morgan, J. J. Aquat. Sci. 1990, 52, 32-55.
(17) Thorn, K. A.; Folan, D. W.; MacCarthy, P. Characterization of
the International Humic Substances Society Standard and
Reference Fulvic and Humic Acids by Solution State Carbon-13
(13C) and Hydrogen-1 (1H) Nuclear Magnetic Resonance Spec-
trometry; Water Resources Investigations Report 89-4196; U.S.
Geological Survey: Denver, 1989.
(18) Mukerjee, P.; Mysels, K. J. Critical Micelle Concentrations of
Aqueous Surfactant Systems; NSRDS-NBS 36; U.S. Department
of Commerce, National Bureau of Standards: Washington, DC,
1970.
(19) Smoluchowski, M. Phys. Z. Phys. Z. 1905, 6, 529-534.
(20) Abramson, H. A. Electrokinetic phenomena and their application
to biology and medicine; ACS Monograph Series 66; Chemical
Catalog Co.: New York, 1934.
(21) Fairbrother, F.; Mastin, H. J. Chem. Soc. 1924, 125, 2319-2330.
(22) Elimelech, M.; Chen, W. H.; Waypa, J. J. Desalination 1994, 95,
269-286.
(23) Childress, A. E.; Elimelech, M. J. Membr. Sci. 1996, 119, 253-
268.
(24) Cadotte, J. E. In Materials Science of Synthetic Membrane; Lloyd,
D. R., Ed.; American Chemical Society: Washington, DC, 1985;
pp 273-294.
(25) Mulder, M. Basic Principles of Membrane Technology; Kluwer
Academic Publishers: Dordrecht, The Netherlands, 1991.
(26) Petersen, R. J. J. Membr. Sci. 1993, 83, 81-150.
(27) Childress, A. E. Ph.D. Dissertation, University of California, Los
Angeles, 1997.
(28) Hunter, R. J. Foundations of Colloid Science, Vol. II; Clarendon
Press: Oxford, 1989.
(29) Dobias, B. In Coagulation and Flocculation; Dobias, B., Ed.;
Marcel Dekker: New York, 1993; pp 539-625.
(30) Hoeft, C. E.; Zollars, R. L. J. Colloid Interface Sci. 1996, 177,
171-178.
(31) Gaudin, M.; Fuerstenau, D. W. AIME Trans. 1955, 202, 958-
962.
(32) Somasundaran, P.; Fuerstenau, D. W. J. Phys. Chem. 1966, 70,
90-96.
(33) Chandar, P.; Somasundaran, P.; Turro, N. J. J. Colloid Interface
Sci. 1987, 117, 31-46.
(34) Gao, Y.; Du, J.; Gu, T. J. Chem. Soc., Faraday Trans. 1 1987, 83,
2671-2679.
(35) Oak, M. S.; Kobayashi, T.; Wang, H. Y.; Fukaya, T.; Fujii N. J.
Membr. Sci. 1997, 123, 185-195.
(36) Hurndall, M. J.; Jacobs, E. P.; Sanderson, R. D. Desalination
1992, 86, 135-154.
(37) Hunter, R. J. Zeta Potential in Colloid Science; Academic Press:
London, 1981.
(38) Moosemiller, M. D.; Hill, C. G., Jr.; Anderson, M. A. Sep. Sci.
Technol. 1989, 24, 641-657.
(39) Nazal, F. F.; Wiesner, M. R. J. Membr. Sci. 1994, 93, 91-103.
(40) Huisman, I. H.; Dutre, B.; Persson, K. M.; Tragardh, G.
Desalination 1997, 113, 95-103.
(41) Faibish, R. S.; Elimelech, M.; Cohen, Y. J. Colloid Interface Sci.
1998, 204, 77-86.
(42) Hoffer, E.; Kedem, O. Desalination 1968, 5, 167-172.
(43) Lonsdale, H. K.; Pusch, W.; Walch, A. J. Chem. Soc., Faraday
Trans. 1 1975, 71, 501-514.
(44) Akred, A. R.; Fane, A. G.; Friend, J. P. In Ultrafiltration Membranes
and Applications; Cooper, A. R., Ed.; Plenum Press: New York,
1980; pp 353-372.
(45) Vonk, M. W.; Smit, J. A. M. J. Colloid Interface Sci. 1983, 96,
121-134.
(46) Tsuru, T.; Urairi, M.; Nakao, S.-I.; Kimura, S. Desalination 1991,
81, 219-227.
(47) Dresner, L. Desalination 1972, 10, 27-46.
(48) Nielsen, D. W.; Jonsson, G. Sep. Sci. Technol. 1994, 29, 1165-
1182.
(49) Lipp, P.; Gimbel, R.; Frimmel, F. H. J. Membr. Sci. 1994, 95,
185-197.
Received for review January 3, 2000. Revised manuscript
received June 7, 2000. Accepted June 12, 2000.
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