membranes

Review
Progress in Research and Application of Nanofiltration (NF)
Technology for Brackish Water Treatment
Jiayu Tian 1 , Xingrui Zhao 1 , Shanshan Gao 1 , Xiaoying Wang 2 and Ruijun Zhang 1, *

1 School of Civil and Transportation Engineering, Hebei University of Technology, Tianjin 300401, China;
tjy800112@163.com (J.T.); zxr18632767623@163.com (X.Z.); gaoshanshan2018@126.com (S.G.)
2 School of Architectural Engineering, Sanming University, Sanming 365004, China; 20151099@fjsmu.edu
* Correspondence: zrj@hebut.edu.cn

Abstract: Brackish water is a potential fresh water resource with lower salt content than seawater.
Desalination of brackish water is an important option to alleviate the prevalent water crisis around
the world. As a membrane technology ranging between UF and RO, NF can achieve the partial
desalination via size exclusion and charge exclusion. So, it has been widely concerned and applied in
treatment of brackish water during the past several decades. Hereon, an overview of the progress
in research on and application of NF technology for brackish water treatment is provided. On the
basis of expounding the features of brackish water, the factors affecting NF efficiency, including the
feed water characteristics, operating conditions and NF membrane properties, are analyzed. For the
ubiquitous membrane fouling problem, three preventive fouling control strategies including feed
water pretreatment, optimization of operating conditions and selection of anti-fouling membranes
are summarized. In addition, membrane cleaning methods for restoring the fouled membrane





 are discussed. Furthermore, the combined utilization of NF with other membrane technologies is
Citation: Tian, J.; Zhao, X.; Gao, S.; reviewed. Finally, future research prospects are proposed to deal with the current existing problems.
Wang, X.; Zhang, R. Progress in Lessons gained from this review are expected to promote the sustainable development of brackish
Research and Application of water treatment with NF technology.
Nanofiltration (NF) Technology for
Brackish Water Treatment. Membranes Keywords: brackish water; NF; desalination; treatment efficiency; combined process; membrane
2021, 11, 662. https://doi.org/ fouling; membrane cleaning
10.3390/membranes11090662

Academic Editors: Xin Li,

Shuaifei Zhao and Yasin Orooji 1. Introduction
The shortage of freshwater has turned into one of the most critical concerns for global
Received: 5 August 2021
Accepted: 25 August 2021
communities, especially for developing countries with a large population. It is estimated
Published: 28 August 2021
that the available freshwater only accounts for 0.8% of the total earth’s water [1]. At
the same time, the deterioration of water quality accompanied by climate change and
Publisher’s Note: MDPI stays neutral
population growth further exacerbates this problem [2]. According to one estimation, 60%
with regard to jurisdictional claims in
of the world’s population will live in water-deficient areas by the year 2025 [3].
published maps and institutional affil- In order to cope with the current water crisis, new sources of freshwater need to be
iations. constantly explored. During the past several decades, many water-deficient countries
have been replenishing freshwater resources with desalinated water to meet the increasing
demand [4]. Seawater accounts for more than 97.5% of the earth’s water resources, so
the desalination of seawater with reverse osmosis (RO) has become the most popular
Copyright: © 2021 by the authors.
choice of many coastal countries [5–8]. However, seawater reverse osmosis (SWRO) has
Licensee MDPI, Basel, Switzerland.
some typical disadvantages, such as high operating costs and low water recovery, which is
This article is an open access article
usually between 30 and 40% [9]. Besides, the highly concentrated brine brings potential
distributed under the terms and hazard to the marine ecological environment [10]. To be different from seawater, brackish
conditions of the Creative Commons water is another important water resource with salinity ranging between fresh water and
Attribution (CC BY) license (https:// seawater [11,12]. As the salinity of brackish water is much lower than that of seawater, the
creativecommons.org/licenses/by/ osmosis pressure of brackish water is much lower than that of seawater, making brackish
4.0/). water desalination even easier and cheaper.

Membranes 2021, 11, 662. https://doi.org/10.3390/membranes11090662 https://www.mdpi.com/journal/membranes

Membranes 2021, 11, 662 2 of 21

On the global scale, the evaporation rate of water is accelerating with global warm-
ing [13], so the salt concentration in the water of some local regions has increased. In
addition, the melting of polar glaciers and rising sea levels cause the backflow of seawater
into some coastal areas and islands [14]. In the low-lying areas with poor rock strata
permeability and long groundwater runoff paths, once salts come into groundwater, the
evaporation and concentration intensify the salt accumulation, thus converting fresh water
into brackish water [15–18]. Furthermore, with the development of economy and industri-
alization, people discharge more and more solid waste and wastewater with high salinity
into the environment. Once the salts in these wastes dissolve and concentrate in a specific
water area, brackish water is also formed. All these factors are expanding the amount
and distribution of brackish water. Taking China as example, brackish water is widely
distributed in the arid areas of the northwest and the coastal areas of the southeast [19].
Globally, brackish water is also widely distributed in many countries, such as Saudi Arabia,
Egypt, Turkey, United States and so on [1]. According to statistics, brackish water accounts
for 1% of the total water on the earth, which is a huge potentially available water resource
to be utilized [20].
Therefore, the desalination of brackish water has become an important approach to
produce safe freshwater. Currently, RO and electrodialysis (ED) are the main technolo-
gies applied in brackish water desalination [21–25]. However, RO and ED have obvious
shortcomings. For example, in the process of RO desalination of brackish water, almost all
ions are removed. Although the harmful ions are rejected, some ions that are beneficial to
body health are also removed [26]. Due to the high driving pressure in the RO desalination
process, its energy consumption is high [27]. The long-term running of full-scale brackish
water RO desalination plants reported by Ruiz-García et al. demonstrated that energy con-
sumption is further increased due to RO membrane fouling [28]. Higher salt concentration
increases the pressure required to produce water due to the osmotic pressure. Moreover,
RO system water recovery is strictly limited by the composition of the inorganic salts in the
feed water, because the scaling ions, such as Ca2+ , Mg2+ , SO4 2− and CO3 2− , form inorganic
precipitants (CaCO3 , CaSO4 , MgCO3 , etc.) that can result in the RO membrane fouling
and deteriorate the treatment efficiency [29,30]. At the same time, the brine produced by
RO requires proper treatment [31]. When brackish water is desalinated by ED, energy
consumption and desalination rate are closely related to the salt content of brackish water.
High salt content obviously increases energy consumption and lowers the desalination rate.
For instance, researching brackish water desalination by ED with a special carbon electrode,
Xu et al. [32] found that the desalination rate decreased with the increase in brackish water
salt concentration. Therefore, ED is more suitable for the desalination of brackish water
with low salinity. In addition, because the organic matter and bacteria in raw water cannot
be removed by ED, its application in the brackish water desalination project is limited.
Nanofiltration (NF) membranes are an effective, pressure-driven membrane sepa-
ration process [33], which was developed in the late 1970s. The nanoscale pores in an
NF membrane are usually less than 2 nm [34] and the molecular weight cut-off (MWCO)
is typically between 150 and 800 Da [35]. NF is a separation process ranging between
ultrafiltration (UF) and RO, which can partially remove the salt in water due to its size
exclusion and charge exclusion [35–37], especially for sulfate and hardness ions [38]. Com-
pared to RO, NF has numerous advantages, such as low operation pressure, low energy
consumption and high throughput [39–42]. The comparison between RO and NF can
be further referenced in a review published by Yang et al. [43]. In consideration of the
features of NF technology, many researchers have carried out a series of studies on the
desalination of brackish water with NF in recent years and explored the effects of different
NF membranes and operating conditions, as well as those of operation modes on treatment
efficiency. Up to now, numerous review papers focusing on the mechanism, application
and development of NF technology have been published [44–47]. However, all these papers
did not take the treatment of brackish water into consideration. Another review published
in 2013 summarized the application and efficiency of NF membranes in the removal of
 in 2013 summarized the application and efficiency of NF membranes in the removal of
ionic components from brackish water, sea water and brine disposal [48]. More recently,
a review involving the improvements in membrane desalination processes for brackish
water was published by Honarparvar et al. [49]. However, various membrane technolo-
Membranesgies, including
2021, 11, 662 RO, NF, ED and membrane capacitive deionization (MCDI), were all dis- 3 of 21
cussed and more attention was given on the separation mechanism. So, it is necessary to
give an overview of the progress in research on and application of brackish water treat-
ment with NF technology. To this end,
ionic components fromthis paperwater,
brackish reviewssea the
waterrelevant practical
and brine disposalcases
[48]. in
More recently,
recent years, analyzes the factors affecting treatment efficiency, the membrane fouling
a review involving the improvements in membrane desalination processes for brackish
problems and the corresponding control
water was published measures, as
by Honarparvar well
et al. [49].asHowever,
the combined
various utilization
membrane technologies,
with other membrane technologies,
including RO, NF,and, finally,
ED and puts forward
membrane capacitive some suggestions
deionization for future
(MCDI), were all discussed
research. and more attention was given on the separation mechanism. So, it is necessary to give an
overview of the progress in research on and application of brackish water treatment with
2. Brackish Water NF technology. To this end, this paper reviews the relevant practical cases in recent years,
analyzes the factors affecting treatment efficiency, the membrane fouling problems and the
Hydrogeologycorresponding
researchers commonly define
control measures, brackish
as well water as utilization
as the combined surface water or membrane
with other
groundwater with the total dissolved
technologies, solids
and, finally, (TDS)
puts in the
forward somerange of 1–25for
suggestions g/L. Theresearch.
future TDS of
brackish water is higher than freshwater (TDS < 1 g/L) and lower than seawater (TDS ~35
2. Brackish
g/L) [1,11]. Underground Water
brackish water is relatively abundant, occupying more than half
of the total groundwaterHydrogeology
storage [50]. researchers commonlywater
Generally, brackish define brackish
with a TDSwater
of 1–5asg/L
surface
is water or
defined as low salinity brackish water, while brackish water with a TDS of 5–10 g/L is The TDS
groundwater with the total dissolved solids (TDS) in the range of 1–25 g/L.
of brackish water is higher than freshwater (TDS < 1 g/L) and lower than seawater (TDS
defined as medium salinity brackish water and brackish water with a TDS over 10 g/L is
~35 g/L) [1,11]. Underground brackish water is relatively abundant, occupying more than
defined as high salinity brackish water. Brackish water tends to exhibit different chemical
half of the total groundwater storage [50]. Generally, brackish water with a TDS of 1–5 g/L
compositions depending on its
is defined geographical
as low location
salinity brackish andwhile
water, the composition ofwith
brackish water the stratum
a TDS of 5–10 g/L is
where it flows through. So, as
defined brackish
medium water canbrackish
salinity also be water
classified into carbonate-type
and brackish water with a brack-
TDS over 10 g/L is
ish water, sulfate-type brackish water and chloride-type brackish water according to its chemical
defined as high salinity brackish water. Brackish water tends to exhibit different
dominant ions, as shown in Figure
compositions 1.
depending on its geographical location and the composition of the stratum
where it flows through. So, brackish water can also be classified into carbonate-type brack-
ish water, sulfate-type brackish water and chloride-type brackish water according to its
dominant ions, as shown in Figure 1.

Figure 1. Chemical classification of brackish water. The common parts of the three-pie chart are K+ ,
Na+ , Ca2+ and Mg2+ , etc.
Figure 1. Chemical classification of brackish water. The common parts of the three-pie chart are K+,
Na+, Ca2+ and Mg2+, etc. Since brackish water is rich in salts such as MgSO4 , CaSO4 and NaCl, it usually exhibits
a bitter, salty and astringent taste. Among them, sulfates such as MgSO4 and NaSO4 play a
Since brackish major
waterrole in thein
is rich bitterness of brackish
salts such as MgSO water. Untreated
4, CaSO 4 and brackish
NaCl, itwater is harmful
usually ex- to human
hibits a bitter, salty and astringent taste. Among them, sulfates such as MgSO4 and NaSO4 cause some
health. Directly drinking untreated brackish water over a long period can
diseases such as digestive disorders, skin infections, dental fluorosis, hypertension, kidney
play a major role in the bitterness of brackish water. Untreated brackish water is harmful
stones and even various cancers [51,52]. Therefore, the quality standards for drinking
to human health. Directly drinking untreated brackish water over a long period can cause
water in different countries all stipulate concentration limits against many salt ions and
some diseases such TDS. as digestive disorders,
Taking China skin infections,
as an example, dental
11 indexes fluorosis,
(Arsenic, hypertension,
Cadmium, Chromium, Fluoride,
Nitrate, Aluminum, Manganese, Chloride, Sulfate, TDS and total hardness) related to salt
ions have been defined in the standards for drinking water quality, as shown in Table 1.
Besides, agricultural irrigation with brackish water for a long time affects the permeability
and water retention properties of the soil, thus inhibiting the growth of crops [53].
Membranes 2021, 11, 662 4 of 21

Table 1. Indicators for drinking water quality established by China.

Indicators Values
Arsenic (mg/L) 0.01
Cadmium (mg/L) 0.005
Chromium (hexavalent, mg/L) 0.05
Fluoride (mg/L) 1.0
Nitrate (in N, mg/L) 10
Aluminum (mg/L) 0.2
Manganese (mg/L) 0.1
Chloride (mg/L) 250
Sulfate (mg/L) 250
TDS (mg/L) 1000
Total hardness (in CaCO3 , mg/L) 450

3. Factors Influencing the Efficiency of Brackish Water Treatment with NF

The efficiency of brackish water treatment with NF technology can be affected by
various factors. These factors can be classified into three categories: characteristics of feed
water, operating conditions and NF membrane properties. The detailed influence of these
factors on the treatment efficiency is summarized and discussed as follows.

3.1. Characteristics of Feed Water

The efficiency of brackish water treatment with NF can be significantly affected by
the characteristics of feed water, such as solution pH and ion composition, as well as
concentration of organic matters. In the research by Song et al. [54], model brackish water
was treated by a commercial NF membrane in which the pH, TDS and TOC of the feed
water were regulated by citric acid, NaOH, inorganic salt and humic acid (HA), respectively.
It was found that, when pH > 6, the removal rate of inorganic salts improved with the
increase in pH. When the TDS was gradually increased from 1 to 4.5 times, the specific
permeate flux decreased by 9.1% and the removal of TDS decreased by 18.21%. With
the increase in TDS, the decreased permeate flux and TDS removal was resulted by the
enhanced concentration polarization and decreased effective trans-membrane pressure.
When the TOC concentration increased from 1 to 4.5 times, the specific permeate flux
declined by 8.78%. Moreover, an interesting phenomenon observed was that the removal of
Mg2+ , Ca2+ and TDS was increased by 74.13%, 48.14% and 20.50%, respectively. Similarly,
Su et al. [55] studied the influence of DOC in feed water on the treatment of model brackish
water by NF. The water quality of the model brackish water was similar to the brackish
groundwater in the Huanghuai region of China. In their research, the DOC was regulated
by changing the HA concentration. It was found that, when the feed DOC increased from
0.54 mg/L to 2.43 mg/L, the specific permeate flux declined by 5.93%, while the growth
in the removal rate of Ca2+ , Mg2+ , SO4 2− and CO3 2− was 47.23%, 58.54%, 98.75% and
82.59%, respectively. It can be explained by the complexation interaction between HA
and Ca2+ [56–58]. On one hand, Ca2+ can partially neutralize the negative charge of HA
molecules [59]. On the other hand, the complexation bridging between HA and Ca2+ can
promote the formation aggregates with larger molecular weights [60]. Consequently, more
organic foulants deposit on the membrane surface and form a more compact cake-layer,
which can produce resistance to the mass transfer of both water and ions [61,62]. With
the increase in HA concentration, the cake layer on the membrane surface was gradually
thickened, resulting in a decrease in specific permeate flux and an increase in ion rejection.
According to the above-discussed cases, the influence of feed water characteristics on
treatment efficiency can be concluded: (1) High solution pH can improve the desalination
rate because of the enhanced charge exclusion between the NF membrane and negatively
charged ions. However, it should be noted that a higher solution pH promotes the precipi-
tation of scaling ions, such as CaCO3 . Besides, strong alkaline condition may damage the
cross-linking structure of NF membranes [63]. (2) High TDS concentration in feed water
reduces the effective trans-membrane pressure and enhances the ion concentration polar-
Membranes 2021, 11, 662 5 of 21

ization, which can obviously decrease the permeate flux and ion rejection. Meanwhile, the
operating pressure would need to be increased to overcome the osmosis pressure induced
by high TDS, which would increase energy consumption and running costs. In addition,
the scaling ions in TDS would increase the formation of inorganic fouling, such as the
precipitation of CaSO4 . Therefore, proper pretreatment may be necessary to remove these
scaling ions and reduce the feed TDS. The influence of pH and salt on the NF separation
process can be further referenced in the review provided by Luo et al. [64]. (3) Although
many studies found that the organic matters in feed water can obviously increase the ion
rejection rate, it should be noted that this enhancement may not be long-term effective. The
membrane fouling induced by organic matters cannot only increase the mass transfer resis-
tance and decrease the water flux, but also reduce the salt rejection via the cake enhanced
concentration polarization (CECP) [65,66]. Therefore, for long-term stable operation, the
influent TOC concentration should not be too high. Pretreatments aiming for the removing
the organic matters in feed water should be taken into consideration.

3.2. Operating Conditions

In addition to the characteristics of feed water, the treatment efficiency can also be
changed by regulating the operating conditions, such as operating pressure, cross-flow
velocity and operating temperature. For instance, Zhang et al. [67] studied the influence
of operating pressure on the treatment of model brackish water with an NF membrane
in which brackish water consisted of 10 g/L NaCl. It was found that the permeate flux
was increased by 58%, when the operating pressure increased from 1.2 MPa to 1.4 MPa.
Meanwhile, the desalination rate was improved from 95% to 97%, when the operating
pressure increased from 1.1 MPa to 1.5 MPa. As the operating pressure increased, the net
driving force of the desalination process increased and so did the permeate flux. However,
according to the solution-diffusion model, the salt permeation process is proportional to
the concentration difference across the membrane, independent of the operating pressure.
Therefore, with the increase in operating pressure, the increase in water permeation dilutes
the ion concentration of the permeate solution and increases the observed salt rejection.
Similarly, Song et al. [68] tested the treatment efficiency of two commercial NF membranes
under different operating conditions. The results showed that the permeate flux and
the removal rate of divalent ions (Ca2+ , Mg2+ ), as well as TDS, were improved with the
increase in operating pressure or cross-flow velocity. At the same time, with the increase in
feedwater temperature (7–35 ◦ C), the permeation flux increased, while the rejection rates
of Ca2+ and Mg2+ decreased greatly. The increase in temperature reduced the viscosity
coefficient of the solution, resulting in the increase in water diffusivity. Therefore, based
on the solution-diffusion model, the permeate flux increased. There are two reasons
for the decreased removal rate of Ca2+ and Mg2+ . On one hand, with the increase in
feedwater temperature, the decrease in pore density and the increase in pore size are
expressed as pore enlargement [69,70]. On the other hand, these structural changes affect
the solute permeation and activation energies of permeation, in which solute permeation is
proportional to pore density [71].
In general, the influence of operating conditions on treatment efficiency can be ob-
tained as follows: (1) Although higher operating pressure can improve permeate flux and
treatment efficiency, it should be noted that membrane fouling would be aggravated once
the permeate flux exceeds a critical value [72]; so, the pressure should not be too high.
(2) Higher cross-flow velocity can reduce the thickness of the boundary layer and mitigate
the concentration polarization, thus reducing membrane fouling [73]. However, excessive
cross-flow velocity would increase energy consumption and may also cause damage to the
selective layer. So, for long-term stable operation, cross-flow velocity should be controlled
at an optimized value. (3) When the feed water temperature is too low, the permeate
flux is small. However, when the temperature is too high, the ion removal rate would be
decreased. Normally, the temperature of feed water should be controlled between 15 and
30 ◦ C.
Membranes 2021, 11, 662 6 of 21

3.3. Properties of NF Membrane

As the core of NF technology, the properties of the NF membrane itself can certainly
influence the efficiency of brackish water treatment. In detail, the pore size and surface
charge of a specific NF membrane are expected to yield different permeate flux and salt
rejection. In previous publications, the famous NF90 and NF270 produced by DOW were
usually employed to study the differences in treatment efficiency. The main characteristics
of NF90 and NF270 are shown in Table 2. The surface of most commercial NF membranes
is negatively charged [74]. So, the removal rate of anion is generally higher because of
the electrostatic repulsion between the negatively charged ion and membrane matrix [68].
The ion rejection rate and permeate flux are also influenced by the membrane pore size.
In general, a low rejection rate is associated with high water permeability, which can be
described as the “trade-off” between water permeability and desalination rate [46].

Table 2. Characteristics of NF 90 and NF270 [75].

Items NF90 NF270

Surface layer material fully aromatic polyamide semi-aromatic polyamide
Water permeability (L/(m2 ·h·bar)) a 9.0 17.5
Salt rejection (%) b 87.4 56.3
Zeta potential (mV) c −13 −53
Contact angle (◦ ) d 55.2 ± 2.5 18.3 ± 2.6
Surface roughness (nm) 64.9 ± 8.1 5.1 ± 0.5
Pore radius (nm) e 0.31 0.40
a Water permeability was recorded after 24 h membrane compaction under the following conditions: 100 psi, 25 ◦ C, 1 L/min, pH of 7.5 and
DI water. b Salt rejection was determined after NaCl was added to the feed tank for 24 h under the following conditions: 100 psi, 25 ◦ C,
1 L/min, pH of 7.5 and 10 mM NaCl. c Zeta potential was measured at pH = 7.5 with 10 mM NaCl as the background electrolyte. d The
contact angle and surface roughness were measured for the vacuum-dried membrane coupons after 24 h exposure in DI water. e The
membrane effective pore radius was calculated according to a solute transport model.

In the study by Hilal et al. [76], NF90 and NF270 were adopted to treat the model
brackish water prepared with NaCl. The results showed that the permeate flux of NF90
was lower than that of NF270. Conversely, the rejection rates of NF90 and NF270 to the
5000 ppm NaCl solution were 95% and 29%, respectively, when the operating pressure
was fixed at 0.9 MPa. The above phenomenon can be explained by the steric hindrance
mechanism, because the pore size of NF90 was smaller than that of NF270, so the permeate
flux was lower, while the rejection rate was higher. Similarly, the removal rate of NF90 for
Na+ , Mg2+ and Ca2+ was significantly higher than that of NF270 [2]. Ramdani et al. [77]
studied the defluorination performance of NF90 and NF270 for the treatment of Algerian
brackish water. They found a similar phenomenon where the permeate flux of NF90 was
lower than that of NF270. However, the difference in removal rates of fluoride ions was not
big, which were 88% and 79% for NF90 and NF270, respectively. Moreover, the fluoride
concentrations of the permeate water were 0.35 mg/L and 0.62 mg/L, respectively. These
two values were both lower than the Algerian standards. Under the circumstances, NF270,
which showed a higher permeate flux and lower TDS removal rate, may be the optimal
selection, because it is expected to yield lower energy consumption and slighter membrane
fouling on the premise of meeting the fluoride removal requirement. This should also be
the principle for the selection of membrane type when treating other brackish water with
NF technology.
Direct design and fabrication of a novel NF membrane is a significant route for
promoting the water treatment efficiency. In fact, substantial efforts have been made in
developing novel and high-performance NF membranes, which can be referenced in the
reviews on this topic [78,79]. However, few relevant reports can be found aiming for
the treatment of brackish water as far as we know. So more research about this issue is
necessary in the future.
Membranes 2021, 11, 662 7 of 21

4. Membrane Fouling Control during the Treatment of Brackish Water with NF

Membrane fouling is an inevitable problem faced by all membrane applications, in-
cluding the treatment of brackish water with NF. In order to mitigate membrane fouling
and keep long-term stable operation, various measures can be taken according to actual
conditions. Membrane fouling refers to the phenomenon that the adsorption and deposi-
tion of rejected foulants (including particles, colloid, inorganic salts, organic matters and
microorganisms) on the membrane surface or in the membrane pores, which can decrease
the permeate flux, change the effluent quality and increase energy consumption and operat-
ing costs [80–82]. In general, NF membrane fouling during the treatment of brackish water
can be reduced by three aspects, including pretreatment and optimization of operating
conditions, as well as the preparation or selection of anti-fouling membrane materials.

4.1. Pretreatment
Membrane fouling is largely affected by the feed water characteristics. In order to
enhance the brackish desalination performance of an NF membrane, feed water should
be pretreated with various technologies to remove some typical foulants; then, membrane
fouling could be mitigated. At present, the commonly used pretreatments for the treatment
of brackish water with NF can be classified into three categories, including conventional
water treatment process, membrane filtration and the adjustment of solution chemistry.
Conventional water treatment processes, including coagulation, adsorption and sand
filtration, can all be taken as the pretreatments of brackish water desalination with NF,
because these processes can remove various components to different extent. Among these
processes, coagulation is the most widely used one [83,84], in which the colloidal matters
and hydrophobic foulants can be effectively removed via the formation and removal of
floc, just as shown in Figure 2a. This method is simple and economical, but it should be
noted that the residual coagulant may inversely aggravate membrane fouling, when the
coagulant dosage is not properly controlled.
Membrane filtration, including MF and UF, is also a good option for pretreatment.
Unlike coagulation, membrane filtration does not require the addition of any chemicals to
remove contaminants. Among them, UF is the most widely used one [85]. As shown in
Figure 2b, UF can reduce membrane fouling by removing the suspended solids, colloids,
bacteria and viruses and even organic matters with high molecular weight, such as proteins
and natural organic matters (NOMs). The high efficiency and stable performance of UF
Membranes 2021, 11, x FOR PEER REVIEW 8 o
make it rather competitive, but the fouling of the UF membrane itself should also be taken
into consideration.

Figure 2. Schematic diagram of pretreatment process for NF: (a) coagulation/NF process; (b) UF/NF
Figure 2. Schematic diagram
process. of pretreatment
Reproduced process from
with permission for NF: (a) coagulation/NF
Reference process;
[86]. Copyright 2020,(b) UF/NF process. Reproduced
Elsevier.
with permission from Reference [86]. Copyright 2020, Elsevier.
Solution chemistry can also obviously influence membrane fouling. So, the regulation
Solution
of solution chemistry chemistry
is another can alsopretreatment
important obviously influence
option. membrane Ca2+ and
fouling.
For instance, So, the regu
2+ tion of solution
Mg with bridging chemistry
effects with humic is another
acid important
and sodium pretreatment
alginate option.
can obviously For instance, C
aggravate
and Mg2+ with bridging effects with humic acid and sodium alginate can obviously agg
vate membrane fouling [87,88], so membrane fouling is expected to be mitigated by
moving Ca2+/Mg2+ or humic acid/sodium alginate. In addition, the solution chemistry c
also be regulated by adjusting the pH. It was found that the charge density of humic a
increased with the increase in pH [62]. Moreover, with increasing pH, the streaming
Membranes 2021, 11, 662 8 of 21

membrane fouling [87,88], so membrane fouling is expected to be mitigated by removing

Ca2+ /Mg2+ or humic acid/sodium alginate. In addition, the solution chemistry can also be
regulated by adjusting the pH. It was found that the charge density of humic acid increased
with the increase in pH [62]. Moreover, with increasing pH, the streaming potential of
the membrane changes from positive to negative, resulting in an increase in electroneg-
ativity [89,90]. So, at a high solution pH, the electrostatic repulsion between humic acid
molecules or between humic acid and membrane can be enhanced, resulting in the miti-
gation of membrane fouling. Sodium alginate also shows a similar phenomenon [91]. At
the same time, BSA is also susceptible to the solution pH and membrane fouling induced
by BSA was found to be most serious at its isoelectric point (IEPBSA = pH 4.7) [92,93].
Therefore, the solution pH should be adjusted to a weak alkaline to prevent the occurrence
of BSA fouling. However, it should be noted that inorganic fouling is also influenced by
the solution pH; a high solution pH aggravates the formation of inorganic precipitants
(such as CaCO3 and Mg (OH)2 ) [94,95]. So, the regulation of the solution chemistry should
be cautiously determined according to the quality features of raw water.

4.2. Optimization of Operating Conditions

Membrane fouling is also closely related to the operating conditions, such as permeate
flux and cross-flow velocity. Numerous studies have shown that membrane fouling can
be aggravated at high pressure and low cross-flow velocity. An important concept related
to the operating condition is the critical flux. In the filtration process, if the permeating
flux does not exceed the critical flux, membrane fouling can be controlled in the rather low
extent. Once the permeating flux exceeds the critical flux, the fouling process is greatly
accelerated [96–99]. Therefore, it is desirable to operate the membrane system below the
critical flux to avoid serious membrane fouling. Moreover, the concentration polarization
increases when cross-flow velocity decreases, because the shear force on the membrane
surface decreases with the decrease in cross-flow velocity [100]. So, improving cross-flow
velocity is an effective strategy for mitigating the membrane fouling, although it can
increase energy consumption.
System water recovery is another critical parameter to be optimized. Higher system
recovery can improve the permeate water yield, while, on the other hand, it can aggravate
the concentration polarization and promote the formation of scaling (inorganic membrane
fouling) on the membrane surface. Calculation predicting is meaningful to the determi-
nation of the water recovery. For instance, a study reported by Mitko et al. assessed the
scaling risk in the treatment of mine brackish water, in which a method for estimating the
maximum water recovery before the occurrence of the calcium sulfate dihydrate scaling
was proposed [101].

4.3. Selection of NF Membranes with Anti-Fouling Ability

Membrane fouling is essentially a kind of physical and chemical phenomenon on the
NF membrane surface. Many researchers have speculated that the properties of the mem-
brane surface could determine the interaction between the membrane and foulants [102].
Therefore, membrane fouling can be effectively alleviated by regulating the features of the
membrane surface [103]. For NF membranes, some studies have found that enhancing hy-
drophilicity or reducing surface charge density and roughness can reduce the accumulation
of foulants; then, the membrane anti-fouling ability can be enhanced [104,105].
In recent years, with the rapid development of material science, a variety of novel
materials have been used to prepare anti-fouling NF membranes. For instance, in the
study by Wu et al. [106], ZIF-8 and GO were employed to synthesize the rGO/ZIF-8
composite nano-materials by hydrothermal method; then, the self-made composite nano-
materials (rGO/ZIF-8) were introduced into the functional layer of an NF membrane by
interface polymerization (IP). The separation and anti-fouling performance of the modified
membrane for treatment of actual brackish water was analyzed. It was found that when
the amount of rGO/ZIF-8 was 0.005 wt%, the hydrophilicity of the modified membrane
 materials have been used to prepare anti-fouling NF membranes. For instance, in the
study by Wu et al. [106], ZIF-8 and GO were employed to synthesize the rGO/ZIF-8 com-
posite nano-materials by hydrothermal method; then, the self-made composite nano-ma-
terials (rGO/ZIF-8) were introduced into the functional layer of an NF membrane by in-
Membranes 2021, 11, 662 terface polymerization (IP). The separation and anti-fouling performance of the modified 9 of 21
membrane for treatment of actual brackish water was analyzed. It was found that when
the amount of rGO/ZIF-8 was 0.005 wt%, the hydrophilicity of the modified membrane
reached the highest level and electronegativity also increased. The organic foulants (BSA,
reached the highest level and electronegativity also increased. The organic foulants (BSA,
SA and HA) were not easy to accumulate on the membrane surface. Correspondingly,
SA and HA) were not easy to accumulate on the membrane surface. Correspondingly, after
after rinsing with deionized water, the flux recovery of the fouled modified membrane
rinsing with deionized water, the flux recovery of the fouled modified membrane was more
was more than 80%, which was much higher than that of the unmodified membrane.
than 80%, which was much higher than that of the unmodified membrane.
Surface modification is another effective strategy for enhancing the membrane anti-
Surface modification is another effective strategy for enhancing the membrane an-
fouling performance [107,108]. For example, in the study by Seman et al. [109], they se-
tifouling performance [107,108]. For example, in the study by Seman et al. [109], they
lected neutral hydrophilic N-vinylpyrrolidone as the monomer and modified the surface
selected neutral hydrophilic N-vinylpyrrolidone as the monomer and modified the sur-
of face
a commercial NF membrane
of a commercial NF membraneby grafting the monomer
by grafting onto the
the monomer surface
onto using the
the surface UV-the
using
photografting polymerization technique to reduce the fouling trend.
UV-photografting polymerization technique to reduce the fouling trend. In the study In the study byby
Zhang et al. [110], a commercially available NF membrane was modified
Zhang et al. [110], a commercially available NF membrane was modified by tannic acid-3- by tannic acid-
3-aminopropyltriethoxysilane
aminopropyltriethoxysilane (TA-APTES) coating and
(TA-APTES) coating andsubsequent
subsequenthorseradish
horseradishperoxidase
peroxi-
dase (HRP) immobilization, as shown in Figure 3, which improved the antifouling
(HRP) immobilization, as shown in Figure 3, which improved the antifouling performance perfor-
mance
of theofNF
themembrane.
NF membrane. However,
However, no relevant
no relevant research research
aimingaiming
for thefor the treatment
treatment of
of brackish
brackish water can be found up to now. Allowing the commonality of
water can be found up to now. Allowing the commonality of membrane surface modifica- membrane surface
modification,
tion, surfacesurface modification
modification wouldwould be promising
be promising in enhancing
in enhancing the antifouling
the antifouling abilityabil-
of NF
itymembranes
of NF membranes
fitting for the purpose of brackish water treatment. More researchresearch
fitting for the purpose of brackish water treatment. More about this
about this
issue issue is necessary
is necessary for futureforstudy.
future study.

Figure 3. Schematic illustration of TA-APTES coating and HRP immobilization on an NF membrane.

Figure 3. Schematic illustration of TA-APTES coating and HRP immobilization on an NF membrane.
Reproduced with permission from Reference [110]. Copyright 2021, Elsevier.
Reproduced with permission from Reference [110]. Copyright 2021, Elsevier.
5. Membrane Cleaning
5. Membrane
MembraneCleaning
fouling can be mitigated rather than being absolutely avoided. Once the
membrane fouling reaches a certain extent, membrane cleaning is necessary. Generally,
the water yield, effluent quality and the pressure drop degree of the membrane can be
used to determine whether the membrane needs to be cleaned. Judgment is mainly based
on the following parameters: (1) under normal feed water pressure, water production
decreases by 10–15%, compared with the normal value, (2) the water quality of produced
water decreases by 10–15% or the salt permeability increases by 10–15% and (3) in order to
maintain normal water production, the operating pressure after temperature correction is
increased by 10–15%.
Membrane cleaning efficiency can be evaluated by membrane permeate flux recovery
(FR) or resistance removal rate (RR), as shown in Equations (1) and (2) [111,112]. Meanwhile,
AFM, SEM, hydrophilicity and FTIR spectroscopy of the NF membrane before and after
cleaning can be used together with FR and RR to more comprehensively evaluate the
cleaning performance.
FR (%) = (jpc /jpi ) × 100 (1)
RR (%) = [(Rf − Rc )/(Rf − Ri )] × 100 (2)
where jp i is the initial permeate flux value of the new compacted membrane, jpc is the
permeate flux after membrane cleaning and Ri , Rf and Rc are the initial resistance, the
resistance after fouling and the resistance after membrane cleaning, respectively.
 Membranes 2021, 11, 662 10 of 21

Membrane cleaning includes physical cleaning, chemical cleaning and enzymatic

cleaning. Among them, for the NF membrane fouled by brackish water, the commonly
used cleaning methods are physical cleaning and chemical cleaning.

5.1. Physical Cleaning

Physical cleaning methods include the hydraulic method, gas-liquid pulse, backwash-
ing, circulating washing and osmotic backwashing. Among them, the hydraulic method
and osmotic backwashing are the most widely used ones in NF desalination of brackish
water [113,114]. The hydraulic method is to remove foulants attached on the membrane
surface by reducing the operating pressure and flushing the membrane surface with an
aqueous solution for a certain time. This method is the simplest, but the membrane per-
meate flux recovery is relatively low and the membrane flux drops rapidly again after
short-term operation. As shown in Figure 4, osmotic backwashing is achieved by adding
a highly concentrated salt solution (HS) to the feed side of the membrane and adding
deionized water (DIW) to the permeate side. A large osmotic pressure driving force is
formed across the membrane to make the water flow from the permeate side to the feed
side. When water passes through the membrane, the driving force promotes the removal
Membranes 2021, 11, x FOR PEER REVIEW 11 of 22
of the foulants on the membrane surface. This is an environmentally friendly cleaning
method with high cleaning efficiency.

Figure 4. Schematic of NF membrane fouling and HS-DOBW cleaning. Reproduced with permission
Figure 4. Schematic of NF membrane fouling and HS-DOBW cleaning. Reproduced with permission
from Reference
from Reference [115]. Copyright
[115]. Copyright 2015, Elsevier.
2015, Elsevier.
5.2. Chemical Cleaning
5.2. Chemical Cleaning
In long-term operation, once physical cleaning cannot restore the membrane flux to the
In long-term operation,
initial value, a chemicalonce physical
cleaning cleaning
method cannot
is used. restorecleaning
Chemical the membrane flux toreagents
uses chemical
the initial value, a chemical cleaning method is used. Chemical cleaning uses chemical
to react with substances that cause membrane fouling to restore membrane flux. Typically,
reagentstheto agents
react with
usedsubstances
for chemicalthat cause membrane
cleaning fouling
include sodium to restore(NaOH),
hydroxide membrane flux.dodecyl
sodium
Typically, the agents
sulfate (SDS), used
sodiumfor ethylenediaminetetraacetic
chemical cleaning include sodium hydroxide
acid (EDTA) (NaOH),
and sodium so-
hypochlorite
dium dodecyl
(NaClO).sulfate (SDS), sodium
The factors affectingethylenediaminetetraacetic
chemical cleaning efficiencyacid
are(EDTA)
shown and sodium
in Figure 5.
hypochlorite (NaClO). The factors affecting chemical cleaning efficiency are shown in Fig-
ure 5.
 In long-term operation, once physical cleaning cannot restore the membrane flux to
the initial value, a chemical cleaning method is used. Chemical cleaning uses chemical
reagents to react with substances that cause membrane fouling to restore membrane flux.
Typically, the agents used for chemical cleaning include sodium hydroxide (NaOH), so-
dium dodecyl sulfate (SDS), sodium ethylenediaminetetraacetic acid (EDTA) and sodium
Membranes 2021, 11, 662 11 of 21
hypochlorite (NaClO). The factors affecting chemical cleaning efficiency are shown in Fig-
ure 5.

Figure 5. The classification of factors affecting chemical cleaning efficiency.

Figure 5. The classification of factors affecting chemical cleaning efficiency
Chemical cleaning has a high cleaning efficiency for organic fouling and biofoul-
ChemicalMany
ing [116,117]. cleaning has have
studies a highshown
cleaningthatefficiency for organic
organic fouling is thefouling
first stepandinbiofouling
NF mem-
[116,117]. Many studies have shown that organic fouling is
brane fouling [118] and it plays an important role in promoting other membrane the first step in NF membrane
fouling
fouling [118]
(inorganic and it colloid
fouling, plays anfouling
importantand role in promoting
biofouling) other The
[119–121]. membrane
cleaning fouling (inor-
of organic
ganic fouling, colloid fouling and biofouling) [119–121]. The cleaning
fouling commonly requires the joint application of lye and surfactant and the cleaning of organic fouling
commonly requires
mechanism the joint
is as follows: Dueapplication
to the highof lye
pHand andsurfactant and the
ionic strength of cleaning
NaOH inmechanism
the alkali
Membranes 2021, 11, x FOR PEER REVIEW is as follows: Due to the high pH and ionic strength of
solution, the counterion concentration around the membrane matrix increases NaOH in the alkali solution,
and 22 the
12 offorms a
counterion concentration around the membrane matrix increases
counterion layer, which causes charge repulsion, then the membrane pores expand. At theand forms a counterion
layer,time,
same which thecauses charge repulsion,
surfactant-sodium then sulfate
dodecyl the membrane
can reduce pores
theexpand. At the
interfacial sameoftime,
tension lye
the surfactant-sodium
and improve its wettingdodecyl sulfatesocan
permeability, thatreduce
lye canthe interfacial
quickly tension
penetrate into ofthelye and im-
interior of
foulant layer.
prove its Finally,
wetting organic matter is that
permeability, saponified caninto soluble substances, which can be
the foulant layer. Finally, organicso matterlye quickly
is saponified penetrate
into into the
soluble substances, interior
which ofcan
the
easily removed. It is worth noting that alkaline washing alone enlarges the membrane
be easily removed. It is worth noting that alkaline washing alone enlarges the membrane
pores, then small solutes are more prone to enter the pores, resulting in more serious pore
pores, then small solutes are more prone to enter the pores, resulting in more serious pore
narrowing effect and membrane fouling, while adding SDS to the alkaline cleaning agents,
narrowing effect and membrane fouling, while adding SDS to the alkaline cleaning agents,
as shown in Figure
as shown 6, SDS
in Figure not only
6, SDS enhances
not only the cleaning
enhances efficiency
the cleaning via its
efficiency viastrong binding
its strong binding
ability, but also offsets the alkali-induced pore swelling to further improve
ability, but also offsets the alkali-induced pore swelling to further improve the antifoulingthe antifouling
performance
performance of theof NF
the membrane
NF membrane [122].
[122].

Figure 6. Illustration of alkaline cleaning and alkaline SDS cleaning for the methyl orange induced
Figure 6. Illustration
membrane of alkaline
fouling. cleaning
Reproduced withand alkaline from
permission SDS cleaning
Referencefor the methyl
[122]. orange
Copyright induced
2021, Elsevier.
membrane fouling. Reproduced with permission from Reference [122]. Copyright 2021, Elsevier.
Due to the complex and diverse composition of membrane fouling, a single cleaning
Due to the
method complex
is usually and diverse
unable composition
to achieve of cleaning
the desirable membrane fouling,Therefore,
efficiency. a single cleaning
in practical
method is usually unable to achieve the desirable cleaning efficiency. Therefore, in prac-
tical engineering, different cleaning methods are often used in combination to better re-
store the performance of NF membranes. Typical examples related to the treatment of
brackish water are shown in Table 3. More information can be found in the review focus-
 Membranes 2021, 11, 662 12 of 21

engineering, different cleaning methods are often used in combination to better restore
the performance of NF membranes. Typical examples related to the treatment of brackish
water are shown in Table 3. More information can be found in the review focusing on the
topic of NF membrane cleaning [123].

Table 3. Typical membrane cleaning examples related to the treatment of brackish water.

NF Membrane Feedwater Cleaning Method Results Reference

FR = 97.80%
DK
2.0 wt.% citric acid + NaOH solution RR = 61.63%
Synthetic brackish water [55]
(pH = 10) FR = 95.40%
DL
RR = 49.35%
Synthetic arsenic-rich Citric acid (pH = 3) + ultrasound (with
NF3A FR = 99.99% [124]
brackish water
Membranes 2021, 11, x FOR PEER REVIEW the power intensity of 1 W/cm2 ) 13 of 2
Hydraulic cleaning + 0.1% NaOH +
NF-1812 Synthetic brackish water FR = 99.20% [113]
0.025 Na-SDS

fact, NF technology can also be combined with other membrane technologies to form dif
6. Combined Utilization of NF with Other Membrane Technology
ferent combined membrane process systems, so as to improve permeate water quality and
water In recovery,
the previous
assection,
well asthe effects ofenergy
reducing feed water characteristics,
consumption andoperating
membraneconditions
fouling. Exam
and membrane properties on the treatment efficiency of brackish water are discussed. In
ples of practical applications are presented below to illustrate the feasibility of the com
fact, NF technology can also be combined with other membrane technologies to form
bined process for desalination of brackish water.
different combined membrane process systems, so as to improve permeate water quality
and water recovery, as well as reducing energy consumption and membrane fouling.
6.1. Combined
Examples Application
of practical of NF and
applications are UF
presented below to illustrate the feasibility of the
combined process for desalination of brackish
In recent years, low-pressure membrane water.processes such as ultrafiltration (UF) and
microfiltration (MF) have been used as pretreatments of NF technology in the treatmen
6.1. Combined Application of NF and UF
of brackish water. In particular, UF membranes are receiving increasing attention due to
In recent years, low-pressure membrane processes such as ultrafiltration (UF) and
their excellent removal efficiency of colloidal particles, macromolecular organic matters
microfiltration (MF) have been used as pretreatments of NF technology in the treatment
bacteria
of brackishand viruses,
water. which can
In particular, UFinduce membrane
membranes fouling
are receiving [125]. For
increasing instance,
attention dueintothe study
by Fan et al. [85], the UF/NF dual-membrane system, as illustrated in
their excellent removal efficiency of colloidal particles, macromolecular organic matters, Figure 7, was ap
plied toand
bacteria treatviruses,
high chlorine
which canbrackish
induce water takenfouling
membrane from the Mount
[125]. Yan. It was
For instance, found tha
in the
the dual-membrane
study by Fan et al. [85],system
the UF/NFhaddual-membrane
a good removal efficiency
system, on organics
as illustrated and7,salts
in Figure was and th
applied
removaltoratetreatofhigh chlorine
chloride wasbrackish waterAlthough
up to 95%. taken from thethe Mountmitigation
fouling Yan. It waseffect
foundof the UF
that the dual-membrane
pretreatment system had aingood
was not mentioned thisremoval
research,efficiency
it can be onanticipated
organics andthat
saltsthe
andUF mem
the removal rate of chloride was up to 95%. Although the fouling
brane pretreatment could reduce the fouling tendency which has been confirmed mitigation effect ofby many
the UF pretreatment was not mentioned in this research, it can be anticipated that the UF
other studies. For example, in the study by Song et al. [126], UF modules were taken a
membrane pretreatment could reduce the fouling tendency which has been confirmed by
the pretreatment
many other studies. ofForseawater.
example, It
in was found
the study bythat
Songthe NF[126],
et al. membrane
UF modulesfouling
werewas
takenobviously
mitigated because the SDI 15 and turbidity of the raw seawater were effectively decreased
as the pretreatment of seawater. It was found that the NF membrane fouling was obviously
after UF pretreatment.
mitigated because the SDI15 and turbidity of the raw seawater were effectively decreased
after UF pretreatment.

Figure 7. Schematic diagram of the UF–NF system.

Figure 7. Schematic diagram of the UF–NF system.
6.2. Combined Application of NF and NF
For brackish
6.2. Combined water withofhigh
Application NF salinity,
and NF the desalination rate of single-stage NF usually
cannot meet the desalination requirements, while the energy consumption of RO treatment
For brackish water with high salinity, the desalination rate of single-stage NF usually
cannot meet the desalination requirements, while the energy consumption of RO treat
ment is high [127,128]. So, the researchers set their sights on the dual-stage NF which in
deed is the combined application of NF and NF. For example, Chen et al. [129] designed
Membranes 2021, 11, 662 13 of 21

is high [127,128]. So, the researchers set their sights on the dual-stage NF which indeed
is the combined application of NF and NF. For example, Chen et al. [129] designed a
dual-stage NF system, as illustrated in Figure 8, to desalinate surface brackish water in
Binhai New Area of Tianjin (TDS > 12,000 mg/L). In this system, the quartz sand filter,
activated carbon filter and UF acted as the pretreatment units. The brackish water after
pretreatment came to the NF–NF unit for desalination. The results show that the salt
content, total hardness and COD of the permeate water of this system were 600 mg/L,
10 mg/L and 1.5 mg/L, respectively. These water quality parameters can meet the “Water
quality standard for non-potable urban use” (GB/T 18920-2002) proposed by China. More
importantly, this dual-stage NF system yields better permeate water quality than the
single-stage NF process and lower energy consumption than the RO process. So, it14has
Membranes 2021, 11, x FOR PEER REVIEW a
of 22
good demonstration and guidance role in this region and similar cases of brackish water
desalination.

Figure 8. Flow chart of two-stage NF process.

Figure 8. Flow chart of two-stage NF process.
6.3. Combined Application of NF and RO
6.3. Combined Application of NF and RO
NF technology can be used together with RO to maximize their respective advantages
NF technology
and achieve the optimalcan effect
be used togetherwater
of brackish withtreatment.
RO to maximize theirpermeate
In this way, respective ad-
water
vantages
quality orand achieve
system water therecovery
optimalcan
effect
beof brackish water
improved. Up to treatment. In this way,
now, four different permeate
forms of NF
water
and RO quality or system
combinations water
have recovery
been can be
proposed, improved.
which Up to now,
can be denoted fourparallel
as the different forms
NF/RO
of NF and
Membranes 2021, 11, x FOR PEER REVIEW
system, the RO combinations have
RO-concentrate-NF been(RO-C-NF),
system proposed, the
which can be denoted system
NF-concentrate-RO as the parallel
15 of 22
(NF-C-
NF/RO system, the RO-concentrate-NF system (RO-C-NF), the NF-concentrate-RO
RO) and the tandem NF–RO system, respectively. The flow diagram of each combination sys-
tem (NF-C-RO) and the
process is shown in Figure 9. tandem NF–RO system, respectively. The flow diagram of each
combination process is shown in Figure 9.
In the parallel NF/RO system illustrated in Figure 9a, brackish water enters the NF
and RO membrane systems at the same time and the filtrate of each membrane system is
collected together to form mixed permeate water. In the RO-C-NF system shown in Figure
9b, the brackish water first enters the RO system; then, the concentrated brine of RO is
treated by the NF membrane. Finally, the permeate water of RO and NF are mixed to form
the permeate water. In the NF-C-RO system shown in Figure 9c, the brackish water first
enters the NF system; then, the concentrated brine of NF is treated by RO. The permeate
water of NF and RO are mixed to form the final permeate water. Cai et al. constructed a
pilot-scale NF-C-RO system to desalinate natural ground brackish water containing high
Sr concentration (10.3 mg/L) in Tanzania [130]. It was found that the NF unit only had a
Sr rejection of 55–67%, while RO can remove almost 100% of Sr, so the mixture of NF
permeate and RO permeate can meet the USEPA guideline of 1.5 mg/L. In the research by
Srivastava et al. [131], TDS removal and water recovery of the three combinations de-
scribed in Figure 9a–c were compared. It was found that the water recovery of the parallel
NF/RO system was the highest. The water recovery of the RO-C-NF system was higher
Figure 9. Schematic
than that diagramsystem.
of the NF-C-RO of four The
hybrid
TDSsystems configuration:
removal rate of the (a) parallel system
RO-C-NF NF/ROwassystem;
the
Figure 9. Schematic diagram of four hybrid systems configuration: (a) parallel NF/RO system; (b)
(b) RO-C-NF
lowest amongsystem;
the (c) NF-C-RO
three system;
combined (d) tandem
systems, NF–RO
while the system.
NF-C-RO system presented the
RO-C-NF system; (c) NF-C-RO system; (d) tandem NF–RO system.
highest TDS rejection.
Another combination form, denoted as tandem NF–RO system, is illustrated in Fig-
ure 9d. In this process, NF technology is indeed taken as the pretreatment of brackish
water desalination with RO, which is expected to prolong the running life of the subse-
quent RO by reducing the scaling tendency. A retrofitting feasibility assessment made by
Membranes 2021, 11, 662 14 of 21

In the parallel NF/RO system illustrated in Figure 9a, brackish water enters the NF
and RO membrane systems at the same time and the filtrate of each membrane system
is collected together to form mixed permeate water. In the RO-C-NF system shown in
Figure 9b, the brackish water first enters the RO system; then, the concentrated brine of RO
is treated by the NF membrane. Finally, the permeate water of RO and NF are mixed to form
the permeate water. In the NF-C-RO system shown in Figure 9c, the brackish water first
enters the NF system; then, the concentrated brine of NF is treated by RO. The permeate
water of NF and RO are mixed to form the final permeate water. Cai et al. constructed a
pilot-scale NF-C-RO system to desalinate natural ground brackish water containing high
Sr concentration (10.3 mg/L) in Tanzania [130]. It was found that the NF unit only had
a Sr rejection of 55–67%, while RO can remove almost 100% of Sr, so the mixture of NF
permeate and RO permeate can meet the USEPA guideline of 1.5 mg/L. In the research by
Srivastava et al. [131], TDS removal and water recovery of the three combinations described
in Figure 9a–c were compared. It was found that the water recovery of the parallel NF/RO
system was the highest. The water recovery of the RO-C-NF system was higher than that
of the NF-C-RO system. The TDS removal rate of the RO-C-NF system was the lowest
among the three combined systems, while the NF-C-RO system presented the highest
TDS rejection.
Another combination form, denoted as tandem NF–RO system, is illustrated in
Figure 9d. In this process, NF technology is indeed taken as the pretreatment of brackish
water desalination with RO, which is expected to prolong the running life of the subsequent
RO by reducing the scaling tendency. A retrofitting feasibility assessment made by Ruiz-
García et al. confirmed that the utilization of NF before RO could effectively promote the
efficiency, permeate quality and economic viability of the plant [132]. Talaeipour et al. [33]
tried three membrane processes, including single NF, single RO and tandem NF–RO system,
to treat brackish water from Qom Province in Iran. After treatment with single NF, single
RO and tandem NF–RO system, the system desalination rates were 50.21%, 72.02% and
78.65%, respectively; the removal rates of Cl− were 21.10%, 43.8% and 63.95%, respectively.

6.4. Combined Application of NF and FO

To be different from many other pressure-driven membrane separation processes,
FO is driven by the osmotic pressure difference across the membrane [133]. High water
recovery rate, high desalination rate and low membrane fouling tendency are typical
advantages of FO technology [134–136]. For this reason, more and more scholars have
applied FO to the desalination of brackish water. For example, Zhao et al. [137] applied
the FO–NF system, as shown in Figure 10, to desalinate brackish water (TDS, 3970 mg/L)
from Lake Mawson, South Australia. In this system, a Na2 SO4 solution was used as the
draw solution. The working process is described as follows: Brackish water first entered
the FO system in which the water molecules came across the FO membrane driven by the
osmosis pressure generated by the high concentration of the Na2 SO4 solution. Meanwhile,
the Na2 SO4 solution was diluted by the permeate water of FO. Then, the diluted Na2 SO4
solution came to the NF system for further desalination. As the Na2 SO4 rejection of the
selected NF membrane (NF270) was rather high, the TDS of permeate water of the NF
process was very low. Moreover, the concentrated water (high concentration of Na2 SO4 ) of
the NF process can be recycled to the FO system as the drawn solution. It was found that
the removal rate of TDS of this FO–NF system was up to 97%. However, when the same
brackish water was directly desalinated with NF270, the TDS removal rate was only 35.5%.
In addition to the higher TDS removal, FO membrane can also effectively remove other
foulants, such as colloidal particles, organic matters and scaling ions. Theoretically, only
Na2 SO4 can appear in the feed water of an NF membrane. So, membrane fouling of the NF
unit is expected to be greatly reduced.
Membranes 2021, 11, x FOR PEER REVIEW 16 of 22

Membranes 2021, 11, x FOR PEER REVIEW 16 of 22

Membranes 2021, 11, 662 15 of 21

Figure 10. Schematic diagram of FO–NF system.

Figure 10. Schematic diagram of FO–NF system.
Figure
6.5. Other10. Combinations
Schematic diagram of FO–NF system.
6.5. Other Combinations
NF technology can also be combined with multiple membrane processes to achieve
6.5. Other Combinations
NFtreatment
technology
efficient of can also be
brackish combined
water. with multiple
For example, Altaee membrane processes atoNF–FO–
et al. [138] proposed achieve
BWRO desalination system to improve the recovery rate of the system (Figure 11).achieve
NF
efficient technology
treatment ofcan also
brackish be combined
water. For with
example, multiple
Altaee membrane
et al. [138] processes
proposed to
a NF–FO–
In this
efficient
system, treatment
BWRO brackish
desalination of system
water brackish water.
firstlytoentered
improveFor example,
thethe unit Altaee
NFrecovery rateetofal.the
to remove [138]
most ofproposed
system (Figure
divalent aions
NF–FO–
11).andIn
BWRO
this desalination
system, brackish system
water to improve
firstly the
entered recovery
the NF rate
unit of
to the
remove
produced the first stage permeate with a relatively low energy consumption. In consider- systemmost (Figure
of 11).
divalent In this
ions
system,
ation brackish
and produced
of the thewater
relatively first
highfirstly
stage entered
TDSpermeate the
with
of the permeate NF aunit toofremove
relatively
water thislow most it of
energy
stage, was divalent
consumption.
mixed with ions and In
the
produced
consideration
BWRO the first
permeate stage
of the
water permeate
relatively
with highwith
much TDSa of
lower relatively
TDS theto lowthe
permeate
form energy
final consumption.
water of this stage,
permeate itInwas
water. consider-
Themixed
con-
with
ation the
of BWRO
the permeate
relatively high water
TDS ofwith
the much
permeate lower
waterTDS ofto form
this
centrated brine of the NF unit was treated by the FO system with NaCl as the draw solu- the
stage, final
it was permeate
mixed withwater.
the
The
BWRO concentrated
permeate brine
water of the
with NF
much unit was
lower treated
TDS to by
form the FO
the system
final
tion. So, the water in the NF brine could be extracted into the NaCl draw solution, which with
permeate NaCl
water. as the
The draw
con-
solution.
centrated
was So, theofwater
brine
then desalinated thebyNF in
thethe
unitRONF
was brine
Thecould
treated
unit. by the
resultsbe show
extracted
FO that into
system with
the the
NaClNaCl
recovery draw
asrate
the of solution,
draw
the solu-
NF–
which
tion. was
So, thethen desalinated
water in the NF by the
brine RO
could unit.
be The results
extracted show
into the
FO–BWRO system for brackish water with salt content of 1–2.4 g/L was up to 90%, which that
NaCl the
drawrecovery
solution,rate of the
which
NF–FO–BWRO
was
was much highersystem
then desalinatedthan bythefor
thebrackish
RO unit.water
conventional The
single with
results
BWROsalt
showcontent
that the
system, of
with1–2.4 g/L rate
recovery
a recovery wasrateupthe
of to 90%,
aroundNF–
which
FO–BWRO was much
system higher
for than
brackish the conventional
water with salt single
content BWRO
of 1–2.4 system,
g/L waswith
up a recovery
to 90%, rate
which
70%. The high recovery rate of the NF–FO–BWRO system can be attributed to the employ-
around
was much 70%. The than
high the
recovery rate of the NF–FO–BWRO system can be attributed to the
ment of FO,higher conventional
which can simultaneously single
concentrate BWRO thesystem,
NF brine withanda recovery
utilize therateROaround
brine.
employment
70%. The highof FO, which
recovery rate can
of thesimultaneously
NF–FO–BWRO concentrate
system canthe NF brine and
be attributed to theutilize
employ- the
RO brine.
ment of FO, which can simultaneously concentrate the NF brine and utilize the RO brine.

Figure 11. Schematic diagram of NF–FO–BWRO system.

Figure 11. Schematic diagram of NF–FO–BWRO system.
7. Conclusions and Future Perspectives
7.Figure 11. Schematic
Conclusions
This paperand diagram
Future
presents of NF–FO–BWRO
Perspectives
a comprehensive system.
review of the research progress and applications
of NF technology
This for brackish
paper presents water treatment
a comprehensive in recent
review years.
of the The application
research development
progress and applica-
7.
andConclusions
advantages and Future
of NF Perspectives
membranes
tions of NF technology for brackishare introduced.
water treatment Then, the definition,
in recent years. Theclassification
application and
de-
This paper
formation presents
of brackish a comprehensive
water are expounded, review of theby
followed research progress
an overall and applica-
discussion on the
tions of NF technology
desalination of brackishfor brackish
water water
with NF treatmentThe
technology. in recent years.
discussion The application
focuses de-
on the factors
affecting the efficiency of brackish water treatment by NF and the membrane fouling that
occurs in the process of brackish water treatment with NF is also briefly discussed. A series
Membranes 2021, 11, 662 16 of 21

of fouling control strategies and cleaning methods are analyzed. Finally, the combined
application of NF with other membrane technologies are reviewed. In order to promote the
sustainable development of brackish water treatment with NF technology, more attention
should be focused on the following in future research:
(1) The characteristics of specific brackish water and the difference in purification ob-
jectives should be taken into account first, when selecting the treatment process.
Moreover, a comprehensive comparison is needed from the perspectives of economy,
technology and environment;
(2) Understanding the membrane fouling mechanism is the foundation of membrane
fouling control, but most of the reported research related to the desalination of brack-
ish water with NF only concerns the treatment efficiency; the analysis of the fouling
mechanism is not sufficient. So, more microscopic membrane characterizations are
necessary to be adopted to promote the deep understanding of membrane fouling;
(3) As the core of NF membrane technology, membrane material should be given more
attention to further improve the permeability, selectivity and stability, as well as
reducing manufacture costs. In addition, membrane fabrication should be “fitting for
purpose” according to the specific brackish water quality and treatment requirements;
(4) The application of NF technology integrated with other emerging water treatment
technologies is expected to further improve the performance of brackish water treat-
ment. For instance, an integrated NF-calcite contactor process proposed by Had-
dad et al. was proved to be a feasible method to effectively remove the undesirable
compounds (particularly manganese (Mn), iron (Fe) and hardness) from groundwa-
ter [139]. Therefore, more novel hybrid brackish water treatment process combination
with NF as core should be explored.
(5) In the process of treating brackish water, a large amount of concentrated brine is
produced. Up to now, most of the concentrated brine has been directly discharged
into the environment, which brings a great potential harm to ecology. So, subsequent
treatment of concentrated brine is an important issue to be focused on in future
research. The high concentration of salt in the brine should be regarded as a resource,
rather than a contaminant.

Author Contributions: Conceptualization, J.T. and R.Z.; investigation, X.Z.; resources, X.Z. and X.W.;
writing—original draft preparation, J.T. and X.Z.; writing—review and editing, R.Z.; visualization,
J.T. and S.G.; supervision, R.Z.; funding acquisition, J.T., S.G., X.W. and R.Z. All authors have read
and agreed to the published version of the manuscript.
Funding: This research was funded by the National Natural Science Foundation of China (No.
51908180 and No. 51908181), the Natural Science Foundation of Hebei Province (No. E2019202011
and No. E2019202012), the Natural Science Foundation of Tianjin City (No. 19JCJQJC63000) and the
Young and Middle-Aged Teachers Education Research Project of Fujian Provincial Department of
Education (No. JAT190728 and B201941).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Du, J.R.; Zhang, X.; Feng, X.; Wu, Y.; Cheng, F.; Ali, M.E.A. Desalination of high salinity brackish water by an NF-RO hybrid
system. Desalination 2020, 491, 114445. [CrossRef]
2. Sari, M.A.; Chellam, S. Relative contributions of organic and inorganic fouling during nanofiltration of inland brackish surface
water. J. Membr. Sci. 2017, 523, 68–76. [CrossRef]
3. Daly, S.; Allen, A.; Koutsos, V.; Semião, A.J.C. Influence of organic fouling layer characteristics and osmotic backwashing
conditions on cleaning efficiency of RO membranes. J. Membr. Sci. 2020, 616, 118604. [CrossRef]
4. Ghaffour, N.; Missimer, T.M.; Amy, G.L. Technical review and evaluation of the economics of water desalination: Current and
future challenges for better water supply sustainability. Desalination 2013, 309, 197–207. [CrossRef]
Membranes 2021, 11, 662 17 of 21

5. Altmann, T.; Das, R. Process improvement of sea water reverse osmosis (SWRO) and subsequent decarbonization. Desalination
2021, 499, 114791. [CrossRef]
6. Delgado-Torres, A.M.; García-Rodríguez, L.; Moral, M.J. Preliminary assessment of innovative seawater reverse osmosis (SWRO)
desalination powered by a hybrid solar photovoltaic (PV)-Tidal range energy system. Desalination 2020, 477, 114247. [CrossRef]
7. Lee, Y.; Lee, Y.; Shin, K.; Lee, J.; Choi, S.; Park, J.; Roh, H. Process modeling and simulation of an SWRO desalination plant: Case
study of Gijang SWRO desalination plant in Korea. Desalin. Water Treat. 2019, 157, 266–273. [CrossRef]
8. Kurihara, M.; Sasaki, T.; Nakatsuji, K.; Kimura, M.; Henmi, M. Low pressure SWRO membrane for desalination in the Mega-ton
Water System. Desalination 2015, 368, 135–139. [CrossRef]
9. Hashim, A.; Hajjaj, M. Impact of desalination plants fluid effluents on the integrity of seawater, with the Arabian Gulf in
perspective. Desalination 2005, 182, 373–393. [CrossRef]
10. Muñoz, I.; Fernández-Alba, A.R. Reducing the environmental impacts of reverse osmosis desalination by using brackish
groundwater resources. Water Res. 2008, 42, 801–811. [CrossRef] [PubMed]
11. Sachit, D.E.; Veenstra, J.N. Analysis of reverse osmosis membrane performance during desalination of simulated brackish surface
waters. J. Membr. Sci. 2014, 453, 136–154. [CrossRef]
12. Porada, S.; Zhao, R.; Wal, A.; Presser, V.; Biesheuvel, P.M. Review on the science and technology of water desalination by
capacitive deionization. Prog. Mater. Sci. 2013, 58, 1388–1442. [CrossRef]
13. Takeshima, A.; Kim, H.; Shiogama, H.; Lierhammer, L.; Scinocca, J.F.; Seland, Y.; Mitchell, D. Global aridity changes due to
differences in surface energy and water balance between 1.5 ◦ C and 2 ◦ C warming. Environ. Res. Lett. 2020, 15, 0940a7. [CrossRef]
14. Jude, P.J.; Dharshini, S.; Vinobaba, M.; Surendran, S.N.; Ramasamy, R. Anopheles culicifacies breeding in brackish waters in Sri
Lanka and implications for malaria control. Malar. J. 2010, 9, 106. [CrossRef] [PubMed]
15. Herrera, C.; Gamboa, C.; Custodio, E.; Jordan, T.; Godfrey, L.; Jódar, J.; Luque, J.A.; Vargas, J.; Sáez, A. Groundwater origin and
recharge in the hyperarid Cordillera de la Costa, Atacama Desert, northern Chile. Sci. Total Environ. 2018, 624, 114–132. [CrossRef]
16. Petrides, B.; Cartwright, I.; Weaver, T.R. The evolution of groundwater in the Tyrrell catchment, south-central Murray Basin,
Victoria, Australia. Hydrogeol. J. 2006, 14, 1522–1543. [CrossRef]
17. Skrzypek, G.; Dogramaci, S.; Grierson, P.F. Geochemical and hydrological processes controlling groundwater salinity of a large
inland wetland of northwest Australia. Chem. Geol. 2013, 357, 164–177. [CrossRef]
18. Liu, Z.; Tan, H.; Brusseau, M.L. Significance of isotopic and geochemical methods to determine the evolution of inland brackish
and bitter water: An example from the Zuli river in the upper reaches of the Yellow River, China. Hydrol. Process. 2021, 35, e14024.
[CrossRef]
19. Gao, X.; Wang, Y.; Li, Y.; Guo, Q. Enrichment of fluoride in groundwater under the impact of saline water intrusion at the salt lake
area of Yuncheng basin, northern China. Environ. Geol. 2007, 53, 795–803. [CrossRef]
20. Greenlee, L.F.; Lawler, D.F.; Freeman, B.D.; Marrot, B.; Moulin, P. Reverse osmosis desalination: Water sources, technology, and
today’s challenges. Water Res. 2009, 43, 2317–2348. [CrossRef]
21. Ruiz-García, A.; Nuez, I. Long-term intermittent operation of a full-scale BWRO desalination plant. Desalination 2020, 489, 114526.
[CrossRef]
22. Dong, H.; Zhao, L.; Zhang, L.; Chen, H.; Gao, C.; Ho, W.S.W. High-flux reverse osmosis membranes incorporated with NaY
zeolite nanoparticles for brackish water desalination. J. Membr. Sci. 2015, 476, 373–383. [CrossRef]
23. Li, M. Optimal plant operation of brackish water reverse osmosis (BWRO) desalination. Desalination 2012, 293, 61–68. [CrossRef]
24. Li, H.; Zou, L. Ion-exchange membrane capacitive deionization: A new strategy for brackish water desalination. Desalination
2011, 275, 62–66. [CrossRef]
25. Larchet, C.; Zabolotsky, V.I.; Pismenskaya, N.; Nikonenko, V.V.; Tskhay, A.; Tastanov, K.; Pourcelly, G. Comparison of different ED
stack conceptions when applied for drinking water production from brackish waters. Desalination 2008, 222, 489–496. [CrossRef]
26. Subramani, A.; DeCarolis, J.; Pearce, W.; Jacangelo, J.G. Vibratory shear enhanced process (VSEP) for treating brackish water
reverse osmosis concentrate with high silica content. Desalination 2012, 291, 15–22. [CrossRef]
27. Saavedra, E.R.; Gotor, A.G.; Báez, S.O.P.; Martín, A.R.; Ruiz-García, A.; González, A.C. Evaluation of the five years operating data
of a RO brackish water desalination plant in Las Palmas, Canary Islands, Spain: A historic case. Desalin. Water Treat. 2013, 51,
4785–4789. [CrossRef]
28. Ruiz-García, A.; Ruiz-Saavedra, E. 80,000 h operational experience and performance analysis of a brackish water reverse osmosis
desalination plant. Assessment of membrane replacement cost. Desalination 2015, 375, 81–88. [CrossRef]
29. Ruiz-García, A.; Nuez, I.; Carrascosa-Chisvert, M.D.; Santana, J.J. Simulations of BWRO systems under different feedwater
characteristics. Analysis of operation windows and optimal operating points. Desalination 2020, 491, 114582. [CrossRef]
30. Karabelas, A.J.; Mitrouli, S.T.; Kostoglou, M. Scaling in reverse osmosis desalination plants: A perspective focusing on develop-
ment of comprehensive simulation tools. Desalination 2020, 474, 114193. [CrossRef]
31. Alghoul, M.A.; Poovanaesvaran, P.; Sopian, K.; Sulaiman, M.Y. Review of brackish water reverse osmosis (BWRO) system designs.
Renew. Sustain. Energy Rev. 2009, 13, 2661–2667. [CrossRef]
32. Xu, P.; Drewes, J.E.; Heil, D.; Wang, G. Treatment of brackish produced water using carbon aerogel-based capacitive deionization
technology. Water Res. 2008, 42, 2605–2617. [CrossRef] [PubMed]
33. Talaeipour, M.; Nouri, J.; Hassani, A.H.; Mahvi, A.H. An investigation of desalination by nanofiltration, reverse osmosis and
integrated (hybrid NF/RO) membranes employed in brackish water treatment. J. Environ. Health Sci. Eng. 2017, 15, 18. [CrossRef]
Membranes 2021, 11, 662 18 of 21

34. Wang, R.; Lin, S. Pore model for nanofiltration: History, theoretical framework, key predictions, limitations, and prospects. J.
Membr. Sci. 2021, 620, 118809. [CrossRef]
35. Mohammad, A.W.; Teow, Y.H.; Ang, W.L.; Chung, Y.T.; Oatley-Radcliffe, D.L.; Hilal, N. Nanofiltration membranes review: Recent
advances and future prospects. Desalination 2015, 356, 226–254. [CrossRef]
36. Song, Y.; Li, X.; Li, C.; Li, J.; Dong, Z.; Zhang, M.; Qi, P.; Bai, X.; Jiang, K. Exploring and comparing the roles of Ca2+ and Mg2+ in
small-sized natural organics-induced charged nanofiltration membrane fouling. Sep. Purif. Technol. 2020, 251, 117415. [CrossRef]
37. Al-Amoudi, A.; Lovitt, R.W. Fouling strategies and the cleaning system of NF membranes and factors affecting cleaning efficiency.
J. Membr. Sci. 2007, 303, 4–28. [CrossRef]
38. Lhassani, A.; Rumeau, M.; Benjelloun, D.; Pontie, M. Selective demineralization of water by nanofiltration Application to the
defluorination of brackish water. Water Res. 2001, 35, 3260–3264. [CrossRef]
39. Lee, S.; Cho, J.; Elimelech, M. Combined influence of natural organic matter (NOM) and colloidal particles on nanofiltration
membrane fouling. J. Membr. Sci. 2005, 262, 27–41. [CrossRef]
40. Wu, Y.; Xia, S.; Dong, B.; Chu, H.; Liu, J. Study on surface water treatment by hybrid sand filtration and nanofiltration. Desalin.
Water Treat. 2013, 51, 5327–5336. [CrossRef]
41. Schaep, J.; Bruggen, B.V.; Uytterhoeven, S.; Croux, R.; Vanlerberghe, F.; Vandecasteele, C.; Wilms, D.; Houtte, E.V.; Vanlerberghe, F.
Removal of hardness from groundwater by nanofiltration. Desalination 1998, 119, 295–301. [CrossRef]
42. Haddada, R.; Ferjani, E.; Roudesli, M.S.; Deratani, A. Properties of cellulose acetate nanofiltration membranes. Application to
brackish water desalination. Desalination 2004, 167, 403–409. [CrossRef]
43. Yang, Z.; Zhou, Y.; Feng, Z.; Rui, X.; Zhang, T.; Zhang, Z. A Review on Reverse Osmosis and Nanofiltration Membranes for Water
Purification. Polymers 2019, 11, 1252. [CrossRef] [PubMed]
44. Bruggen, B.V.; Mänttäri, M.; Nyström, M. Drawbacks of applying nanofiltration and how to avoid them: A review. Sep. Purif.
Technol. 2008, 63, 251–263. [CrossRef]
45. Oatley-Radcliffe, D.L.; Walters, M.; Ainscough, T.J.; Williams, P.M.; Mohammad, A.W.; Hilal, N. Nanofiltration membranes and
processes: A review of research trends over the past decade. J. Water Process. Eng. 2017, 19, 164–171. [CrossRef]
46. Zhang, R.; Tian, J.; Gao, S.; Bruggen, B.V. How to coordinate the trade-off between water permeability and salt rejection in
nanofiltration? J. Mater. Chem. A 2020, 8, 8831–8847. [CrossRef]
47. Hilal, N.; Al-Zoubi, H.; Darwish, N.A.; Mohamma, A.W.; Arabi, M.A. A comprehensive review of nanofiltration membranes:
Treatment, pretreatment, modelling, and atomic force microscopy. Desalination 2004, 170, 281–308. [CrossRef]
48. Diawara, C.K. Nanofiltration Process Efficiency in Water Desalination. Sep. Purif. Rev. 2008, 37, 303–325. [CrossRef]
49. Honarparvar, S.; Zhang, X.; Chen, T.; Alborzi, A.; Afroz, K.; Reible, D. Frontiers of Membrane Desalination Processes for Brackish
Water Treatment: A Review. Membranes 2021, 11, 246. [CrossRef] [PubMed]
50. Badruzzaman, M.; Subramani, A.; DeCarolis, J.; Pearce, W.; Jacangelo, J.G. Impacts of silica on the sustainable productivity of
reverse osmosis membranes treating low-salinity brackish groundwater. Desalination 2011, 279, 210–218. [CrossRef]
51. Pak, C.Y.C.; Zerwekh, J.E.; Antich, P. Anabolic effects of fluoride on bone. Trends Endocrinol. Metab. 1995, 6, 229–234. [CrossRef]
52. Ortiz, J.M.; Sotoca, J.A.; Expósito, E.; Gallud, F.; García-García, V.; Montiel, V.; Aldaz, A. Brackish water desalination by
electrodialysis: Batch recirculation operation modeling. J. Membr. Sci. 2005, 252, 65–75. [CrossRef]
53. He, K.; Yang, Y.; Yang, Y.; Chen, S.; Hu, Q.; Liu, X.; Gao, F. HYDRUS Simulation of Sustainable Brackish Water Irrigation in a
Winter Wheat-Summer Maize Rotation System in the North China Plain. Water 2017, 9, 536. [CrossRef]
54. Song, Y.; Zhao, G.; Li, T.; Qin, W. Influence of feedwater quality on nanofiltration membrane softening efficiencies for brackish
water in long-term operation. CIESC J. 2017, 68, 3133–3140.
55. Su, X.; Song, Y.; Li, T.; Gao, C. Effect of feed water characteristics on nanofiltration separating performance for brackish water
treatment in the Huanghuai region of China. J. Water Process. Eng. 2017, 19, 147–155. [CrossRef]
56. Hering, J.G.; Morel, F.M.M. Humic acid complexation of calcium and copper. Environ. Sci. Technol. 1988, 22, 1234–1237. [CrossRef]
[PubMed]
57. Wang, Y.; Combe, C.; Clark, M.M. The effects of pH and calcium on the diffusion coefficient of humic acid. J. Membr. Sci. 2001,
183, 49–60. [CrossRef]
58. Sousa, V.S.; Teixeira, M.R. Silver nanoparticles separation from the water using nanofiltration membranes: The role of mono-
divalent salts and NOM. Sep. Purif. Technol. 2015, 149, 165–173. [CrossRef]
59. Tang, C.Y.; Kwon, Y.N.; Leckie, J.O. The role of foulant-foulant electrostatic interaction on limiting flux for RO and NF membranes
during humic acid fouling—Theoretical basis, experimental evidence, and AFM interaction force measurement. J. Membr. Sci.
2009, 326, 526–532. [CrossRef]
60. Tiller, C.L.; O’Melia, C.R. Natural organic matter and colloidal stability: Models and measurements. Colloids Surf. A Physicochem.
Eng. Asp. 1993, 73, 89–102. [CrossRef]
61. Hong, S.; Elimelech, M. Chemical and physical aspects of natural organic matter (NOM) fouling of nanofiltration membranes. J.
Membr. Sci. 1997, 132, 159–181. [CrossRef]
62. Tang, C.Y.; Kwon, Y.N.; Leckie, J.O. Fouling of reverse osmosis and nanofiltration membranes by humic acid-Effects of solution
composition and hydrodynamic conditions. J. Membr. Sci. 2007, 290, 86–94. [CrossRef]
63. Nanda, D.; Tung, K.L.; Li, Y.L.; Lin, N.J.; Chuang, C.J. Effect of pH on membrane morphology, fouling potential, and filtration
performance of nanofiltration membrane for water softening. J. Membr. Sci. 2010, 349, 411–420. [CrossRef]
Membranes 2021, 11, 662 19 of 21

64. Luo, J.; Wan, Y. Effects of pH and salt on nanofiltration—A critical review. J. Membr. Sci. 2013, 438, 18–28. [CrossRef]
65. Mahlangu, T.O.; Hoek, E.M.V.; Mamba, B.B.; Verliefde, A.R.D. Influence of organic, colloidal and combined fouling on NF rejection
of NaC1 and carbamazepine: Role of solute-foulant-membrane interactions and cake-enhanced concentration polarisation. J.
Membr. Sci. 2014, 471, 35–46. [CrossRef]
66. Kim, S.; Lee, S.; Lee, E.; Sarper, S.; Kim, C.H.; Cho, J. Enhanced or reduced concentration polarization by membrane fouling in
seawater reverse osmosis (SWRO) processes. Desalination 2009, 247, 162–168. [CrossRef]
67. Zhang, X.; Wang, J.; Zhao, X.; Du, C.; Yan, W.; Wang, J.; Du, R. Study on desalination of high salinity brackish water for drinking
water production with a domestic nanofiltration membrane. Membr. Sci. Technol. 2020, 40, 87–91. (In Chinese)
68. Song, Y.; Li, T.; Zhou, J.; Li, Z.; Gao, C. Analysis of nanofiltration membrane performance during softening process of simulated
brackish groundwater. Desalination 2016, 399, 159–164. [CrossRef]
69. Mehdizadeh, H.; Dickson, J.M.; Eriksson, P.K. Temperature effects on the performance of thin-film composite, aromatic polyamide
membranes. Ind. Eng. Chem. Res. 1989, 28, 814–824. [CrossRef]
70. Ventresque, C.; Turner, G.; Bablon, G. Nanofiltration: From prototype to full scale. J. Am. Water Works Assoc. 1997, 89, 65–76.
[CrossRef]
71. Sharma, R.; Chellam, S. Temperature Effects on the Morphology of Porous Thin Film Composite Nanofiltration Membranes.
Environ. Sci. Technol. 2005, 39, 5022–5030. [CrossRef]
72. Bacchin, P.; Aimar, P.; Sanchez, V. Model for Colloidal Fouling of Membranes. AIChE J. 1995, 41, 368–376. [CrossRef]
73. Andrade, L.H.; Aguiar, A.O.; Pires, W.L.; Grossi, L.B.; Amaral, M.C.S. Comprehensive bench-and pilot-scale investigation of NF
for gold mining effluent treatment: Membrane performance and fouling control strategies. Sep. Purif. Technol. 2017, 174, 44–56.
[CrossRef]
74. Paugam, L.; Diawara, C.K.; Schlumpf, J.P.; Jaouen, P.; Quéméneur, F. Transfer of monovalent anions and nitrates especially
through nanofiltration membranes in brackish water conditions. Sep. Purif. Technol. 2004, 40, 237–242. [CrossRef]
75. Zhao, H.; Yang, L.; Chen, X.; Sheng, M.; Cao, G.; Cai, L.; Meng, S.; Tang, C.Y. Degradation of Polyamide Nanofiltration
Membranes by Bromine: Changes of Physiochemical Properties and Filtration Performance. Environ. Sci. Technol. 2021, 55,
6329–6339. [CrossRef]
76. Hilal, N.; Al-Zoubi, H.; Mohammad, A.W.; Darwish, N.A. Nanofiltration of highly concentrated salt solutions up to seawater
salinity. Desalination 2005, 184, 315–326. [CrossRef]
77. Ramdani, A.; Deratani, A.; Taleb, S.; Drouiche, N.; Lounici, H. Desalination and Water Treatment Performance of NF90 and NF270
commercial nanofiltration membranes in the defluoridation of Algerian brackish water. Desalin. Water Treat. 2021, 212, 286–296.
[CrossRef]
78. Paul, M.; Jons, S.D. Chemistry and fabrication of polymeric nanofiltration membranes: A review. Polymer 2016, 103, 417–456.
[CrossRef]
79. Alsayed, A.F.M.; Ashraf, M.A. Modified nanofiltration membrane treatment of saline water: A review. Desalin. Water Treat. 2020,
187, 93–105. [CrossRef]
80. Klaysom, C.; Cath, T.Y.; Depuydt, T.; Vankelecom, I.F.J. Forward and pressure retarded osmosis: Potential solutions for global
challenges in energy and water supply. Chem. Soc. Rev. 2013, 42, 6959–6989. [CrossRef] [PubMed]
81. Bartels, C.R.; Wilf, M.; Andes, K.; Iong, J. Design considerations for wastewater treatment by reverse osmosis. Water Sci. Technol.
2005, 51, 473–482. [CrossRef]
82. Heidari, S.; Amirinejad, M.; Mirzadeh, S.S.; Wood, D.A. Insights into colloidal membrane fouling mechanisms for nanofiltration
of surface water using single and hybrid membrane processes. Polym. Adv. Technol. 2021, 32, 2517–2530. [CrossRef]
83. Ang, W.L.; Mohammad, A.W.; Benamor, A.; Hilal, N.; Leo, C.P. Hybrid coagulation-NF membrane process for brackish water
treatment: Effect of antiscalant on water characteristics and membrane fouling. Desalination 2016, 393, 144–150. [CrossRef]
84. Elazhar, F.; Elazhar, M.; Filali, N.E.; Belhamidi, S.; Elmidaoui, A.; Taky, M. Potential of hybrid NF-RO system to enhance chloride
removal and reduce membrane fouling during surface water desalination. Sep. Purif. Technol. 2021, 261, 118299. [CrossRef]
85. Fan, G.; Li, Z.; Yan, Z.; Wei, Z.; Xiao, Y.; Chen, S.; Shang, H.; Lin, H.; Chang, H. Operating parameters optimization of combined
UF/NF dual-membrane process for brackish water treatment and its application performance in municipal drinking water
treatment plant. J. Water Process. Eng. 2020, 38, 101547. [CrossRef]
86. Wang, J.; Tang, X.; Xu, Y.; Cheng, X.; Li, G.; Liang, H. Hybrid UF/NF process treating secondary effluent of wastewater treatment
plants for potable water reuse: Adsorption vs. coagulation for removal improvements and membrane fouling alleviation. Environ.
Res. 2020, 188, 109833. [CrossRef]
87. Zhang, H.; Tian, J.; Hao, X.; Liu, D.; Cui, F. Investigations on the fouling characteristic of humic acid and alginate sodium in
capacitive deionization. J. Water Reuse Desalin. 2021, 11, 160–176. [CrossRef]
88. Vicini, S.; Mauri, M.; Wichert, J.; Castellano, M. Alginate gelling process: Use of bivalent ions rich microspheres. Polym. Eng. Sci.
2017, 57, 531–536. [CrossRef]
89. Teixeira, M.R.; Rosa, M.J.; Nyström, M. The role of membrane charge on nanofiltration performance. J. Membr. Sci. 2005, 265,
160–166. [CrossRef]
90. Mänttäri, M.; Pihlajamäki, A.; Nyström, M. Effect of pH on hydrophilicity and charge and their effect on the filtration efficiency
of NF membranes at different pH. J. Membr. Sci. 2006, 280, 311–320. [CrossRef]
Membranes 2021, 11, 662 20 of 21

91. Ang, W.S.; Lee, S.; Elimelech, M. Chemical and physical aspects of cleaning of organic-fouled reverse osmosis membranes. J.
Membr. Sci. 2006, 272, 198–210. [CrossRef]
92. Ang, W.S.; Elimelech, M. Protein (BSA) fouling of reverse osmosis membranes: Implications for wastewater reclamation. J. Membr.
Sci. 2007, 296, 83–92. [CrossRef]
93. Mo, H.; Tay, K.G.; Ng, H.Y. Fouling of reverse osmosis membrane by protein (BSA): Effects of pH, calcium, magnesium, ionic
strength and temperature. J. Membr. Sci. 2008, 315, 28–35. [CrossRef]
94. Eichinger, S.; Boch, R.; Leis, A.; Koraimann, G.; Grengg, C.; Domberger, G.; Nachtnebel, M.; Schwab, C.; Dietzel, M. Scale deposits
in tunnel drainage systems—A study on fabrics and formation mechanisms. Sci. Total Environ. 2020, 718, 137140. [CrossRef]
95. Andreeva, M.A.; Gil, V.V.; Pismenskaya, N.D.; Dammak, L.; Kononenko, N.A.; Larchet, C.; Grande, D.; Nikonenko, V.V. Mitigation
of membrane scaling in electrodialysis by electroconvection enhancement, pH adjustment and pulsed electric field application. J.
Membr. Sci. 2018, 549, 129–140. [CrossRef]
96. Field, R.W.; Pearce, G.K. Critical, sustainable and threshold fluxes for membrane filtration with water industry applications. Adv.
Colloid Interface Sci. 2011, 164, 38–44. [CrossRef] [PubMed]
97. Bacchin, P.; Aimar, P.; Field, R.W. Critical and sustainable fluxes: Theory, experiments and applications. J. Membr. Sci. 2006, 281,
42–69. [CrossRef]
98. Lewis, W.J.T.; Mattsson, T.; Chew, Y.M.J.; Bird, M.R. Investigation of cake fouling and pore blocking phenomena using fluid
dynamic gauging and critical flux models. J. Membr. Sci. 2017, 533, 38–47. [CrossRef]
99. Field, R.W.; Wu, D.; Howell, J.A.; Gupta, B.B. Critical flux concept for microfiltration fouling. J. Membr. Sci. 1995, 100, 259–272.
[CrossRef]
100. Braghetta, B.A.; DiGiano, F.A.; Ball, W.P. NOM Accumulation at NF Membrane Surface: Impact of Chemistry and Shear. J.
Environ. Eng. 1998, 124, 1087–1098. [CrossRef]
101. Mitko, K.; Laskowska, E.; Turek, M.; Dydo, P.; Piotrowski, K. Scaling Risk Assessment in Nanofiltration of Mine Waters. Membranes
2020, 10, 288. [CrossRef]
102. Jones, K.L.; O’Melia, C.R. Protein and humic acid adsorption onto hydrophilic membrane surfaces: Effects of pH and ionic
strength. J. Membr. Sci. 2000, 165, 31–46. [CrossRef]
103. Matin, A.; Khan, Z.; Zaidi, S.M.; Boyce, M.C. Biofouling in reverse osmosis membranes for seawater desalination: Phenomena
and prevention. Desalination 2011, 281, 1–16. [CrossRef]
104. Tang, C.Y.; Fu, Q.S.; Criddle, C.S.; Leckie, J.O. Effect of Flux (Transmembrane Pressure) and Membrane Properties on Fouling and
Rejection of Reverse Osmosis and Nanofiltration Membranes Treating Perfluorooctane Sulfonate Containing Wastewater. Environ.
Sci. Technol. 2007, 41, 2008–2014. [CrossRef] [PubMed]
105. Vrijenhoek, E.M.; Hong, S.; Elimelech, M. Influence of membrane surface properties on initial rate of colloidal fouling of reverse
osmosis and nanofiltration membranes. J. Membr. Sci. 2001, 188, 115–128. [CrossRef]
106. Wu, H. Preparation of rGO/ZIF-8 Modified Nanofiltration Membrane and Experimental Study on Desalination of Brackish Water.
Master’s Thesis, Xi’an University of Architecture and Technology, Xi’an, China, 2020. (In Chinese)
107. Ayyavoo, J.; Nguyen, T.P.N.; Jun, B.M.; Kim, I.C.; Kwon, Y.N. Protection of polymeric membranes with antifouling surfacing via
surface modifications. Colloids Surf. A Physicochem. Eng. Asp. 2016, 506, 190–201. [CrossRef]
108. Zhou, M.; Chen, J.; Zhou, W.; Sun, J.; Tang, H. Developing composite nanofiltration membranes with highly stable antifouling
property based on hydrophilic roughness. Sep. Purif. Technol. 2021, 256, 117799. [CrossRef]
109. Seman, M.N.A.; Hilal, N.; Khayet, M. UV-photografting modification of NF membrane surface for NOM fouling reduction.
Desalin. Water Treat. 2013, 51, 4855–4861. [CrossRef]
110. Zhang, J.; Zhou, F.; Li, S.; Wan, Y.; Luo, J. Surface functionalization of nanofiltration membrane by catechol-amine codeposition
for enhancing antifouling performance. J. Membr. Sci. 2021, 635, 119451. [CrossRef]
111. Song, Y.; Su, B.; Gao, X.; Gao, C. The performance of polyamide nanofiltration membrane for long-term operation in an integrated
membrane seawater pretreatment system. Desalination 2012, 296, 30–36. [CrossRef]
112. Chong, T.H.; Wong, F.S.; Fane, A.G. Enhanced concentration polarization by unstirred fouling layers in reverse osmosis: Detection
by sodium chloride tracer response technique. J. Membr. Sci. 2007, 287, 198–210. [CrossRef]
113. Li, X. Study on the Performance of Nanofiltration Membrane Fouling by Natural Organic Matter. Master’s Thesis, Lanzhou
Jiaotong University, Lanzhou, China, 2019. (In Chinese)
114. Dana, A.; Hadas, S. Ramon, G.Z. Potential application of osmotic backwashing to brackish water desalination membranes.
Desalination 2019, 468, 114029. [CrossRef]
115. Jiang, W.; Wei, Y.; Gao, X.; Gao, C.; Wang, Y. An innovative backwash cleaning technique for NF membrane in groundwater
desalination: Fouling reversibility and cleaning without chemical detergent. Desalination 2015, 359, 26–36. [CrossRef]
116. Yu, T.; Meng, L.; Zhao, Q.B.; Shi, Y.; Hu, H.Y.; Lu, Y. Effects of chemical cleaning on RO membrane inorganic, organic and
microbial foulant removal in a full-scale plant for municipal wastewater reclamation. Water Res. 2017, 113, 1–10. [CrossRef]
[PubMed]
117. Tin, M.M.M.; Anioke, G.; Nakagoe, O.; Tanabe, S.; Kodamatani, H.; Nghiem, L.D.; Fujioka, T. Membrane fouling, chemical
cleaning and separation performance assessment of a chlorine-resistant nanofiltration membrane for water recycling applications.
Sep. Purif. Technol. 2017, 189, 170–175. [CrossRef]
Membranes 2021, 11, 662 21 of 21

118. Zheng, X.; Khan, M.T.; Cao, X.; Croue, J.P. Importance of origin and characteristics of biopolymers in reversible and irreversible
fouling of ultrafiltration membranes. Sci. Total Environ. 2021, 784, 147157. [CrossRef]
119. Her, N.; Amy, G.; Plottu-Pecheux, A.; Yoon, Y. Identification of nanofiltration membrane foulants. Water Res. 2007, 41, 3936–3947.
[CrossRef]
120. Tran, T.; Bolto, B.; Gray, S.; Hoang, M.; Ostarcevic, E. An autopsy study of a fouled reverse osmosis membrane element used in a
brackish water treatment plant. Water Res. 2007, 41, 3915–3923. [CrossRef]
121. Cho, J.; Amy, G.; Pellegrino, J.; Yoon, Y. Characterization of clean and natural organic matter (NOM) fouled NF and UF membranes,
and foulants characterization. Desalination 1998, 118, 101–108. [CrossRef]
122. Huang, J.; Luo, J.; Chen, X.; Feng, S.; Wan, Y. New insights into effect of alkaline cleaning on fouling behavior of polyamide
nanofiltration membrane for wastewater treatment. Sci. Total Environ. 2021, 780, 146632. [CrossRef]
123. Liu, Z.; Cao, J.; Li, C.; Meng, H. A review on cleaning of nanofiltration and reverse osmosis membranes used for water treatment.
Desalin. Water Treat. 2017, 87, 27–67. [CrossRef]
124. Wang, J.; Gao, X.; Xu, Y.; Wang, Q.; Zhang, Y.; Wang, X.; Gao, C. Ultrasonic-assisted acid cleaning of nanofiltration membranes
fouled by inorganic scales in arsenic-rich brackish water. Desalination 2016, 377, 172–177. [CrossRef]
125. Tomaszewska, B.; Bodzek, M. Desalination of geothermal waters using a hybrid UF-RO process. Part II: Membrane scaling after
pilot-scale tests. Desalination 2013, 319, 107–114. [CrossRef]
126. Song, Y.; Xu, J.; Xu, Y.; Gao, X.; Gao, C. Performance of UF-NF integrated membrane process for seawater softening. Desalination
2011, 276, 109–116. [CrossRef]
127. Anand, A.; Unnikrishnan, B.; Mao, J.Y.; Lin, H.J.; Huang, C.C. Graphene-based nanofiltration membranes for improving salt
rejection, water flux and antifouling—A review. Desalination 2018, 429, 119–133. [CrossRef]
128. Liu, M.; He, Q.; Guo, Z.; Zhang, K.; Yu, S.; Gao, C. Composite reverse osmosis membrane with a selective separation layer of
double-layer structure for enhanced desalination, anti-fouling and durability properties. Desalination 2021, 499, 114838. [CrossRef]
129. Chen, X.; Zhao, H.; Wang, L.; Fu, X. Application of two stages nanofiltration in desalting of high degree brackish water. Membr.
Sci. Technol. 2013, 33, 63–67. (In Chinese)
130. Cai, Y.; Yang, X.; Schäfer, A.I. Removal of Naturally Occurring Strontium by Nanofiltration/Reverse Osmosis from Groundwater.
Membranes 2020, 10, 321. [CrossRef] [PubMed]
131. Srivastava, A.; Aghilesh, K.; Nair, A.; Ram, S.; Agarwal, S.; Ali, J.; Singh, R.; Garg, M.C. Response surface methodology and
artificial neural network modelling for the performance evaluation of pilot-scale hybrid nanofiltration (NF) & reverse osmosis
(RO) membrane system for the treatment of brackish ground water. J. Environ. Manag. 2021, 278, 111497.
132. Ruiz-García, A.; Dimitriou, E.; Nuez, I. Retrofitting assessment of a full-scale brackish water reverse osmosis desalination plant
with a feed capacity of 600 m3 /d. Desalin. Water Treat. 2019, 144, 72–78. [CrossRef]
133. Gwak, G.; Hong, S. New approach for scaling control in forward osmosis (FO) by using an antiscalant-blended draw solution. J.
Membr. Sci. 2017, 530, 95–103. [CrossRef]
134. Zhao, S.; Zou, L.; Tang, C.Y.; Mulcahy, D. Recent developments in forward osmosis: Opportunities and challenges. J. Membr. Sci.
2012, 396, 1–21. [CrossRef]
135. Xie, M.; Lee, J.; Nghiem, L.D.; Elimelech, M. Role of pressure in organic fouling in forward osmosis and reverse osmosis. J. Membr.
Sci. 2015, 493, 748–754. [CrossRef]
136. Chun, Y.; Zaviska, F.; Kim, S.J.; Mulcahy, D.; Yang, E.; Kim, I.S.; Zou, L. Fouling characteristics and their implications on cleaning
of a FO-RO pilot process for treating brackish surface water. Desalination 2016, 394, 91–100. [CrossRef]
137. Zhao, S.; Zou, L.; Mulcahy, D. Brackish water desalination by a hybrid forward osmosis-nanofiltration system using divalent
draw solute. Desalination 2012, 284, 175–181. [CrossRef]
138. Altaee, A.; Hilal, N. High recovery rate NF-FO-RO hybrid system for inland brackish water treatment. Desalination 2015, 363,
19–25. [CrossRef]
139. Haddad, M.; Barbeau, B. Hybrid Hollow Fiber Nanofiltration-Calcite Contactor: A Novel Point-of-Entry Treatment for Removal
of Dissolved Mn, Fe, NOM and Hardness from Domestic Groundwater Supplies. Membranes 2019, 9, 90. [CrossRef] [PubMed]