Desalination 441 (2018) 96–111

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Brine pre-treatment technologies for zero liquid discharge systems T

⁎
Galilee Uy Semblante, Jonathan Zhiqiang Lee, Lai Yoke Lee, Say Leong Ong, How Yong Ng
Sembcorp-NUS Corporate Laboratory, National University of Singapore, Faculty of Engineering, Block E1A, #04-01, 1 Engineering Drive 2, Singapore 117576, Singapore
Centre for Water Research, Department of Civil & Environmental Engineering, Faculty of Engineering, National University of Singapore, Singapore, Block E1A, #07-01, 1
Engineering Drive 2, Singapore 117576, Singapore

A R T I C LE I N FO A B S T R A C T

Keywords: The management of brine produced by the reverse osmosis process is challenging due to its high salt and organic
Zero liquid discharge content. Limitations in brine disposal options sometimes necessitate the use of zero liquid discharge (ZLD)
Antiscalant approach. ZLD systems may include a membrane process – which is used to recover water and to further con-
Electrocoagulation centrate brine – followed by thermal treatment. In such systems, a high-water recovery rate is difficult to achieve
Ion exchange
due to the early onset of membrane scaling and fouling. Brine pre-treatment is therefore necessary to protect the
Nanofiltration
membrane and facilitate ZLD. Literature shows that the most common brine pre-treatment process, chemical
Precipitation
precipitation, is generally costly because of high chemical consumption and hazardous sludge production.
Moreover, its performance may be hindered by the temporal fluctuations in brine chemistry and the occurrence
of residual antiscalants in the brine. A critical evaluation of alternative pre-treatment options was performed. It
was found that electrocoagulation and nanofiltration processes have promising performance in terms of hardness
and organic removals. Meanwhile, coagulation and adsorption processes show potential for organic removal.
Further studies should be performed on process optimization and cost analysis to determine the feasibility of
applying these technologies in ZLD systems.

1. Introduction RO, electrodialysis (ED)/electodialysis reversal (EDR), membrane dis-

Brine is a highly concentrated reject stream produced by the reverse
osmosis (RO) process in water purification applications such as desa-
lination or water reuse. The management of brine is traditionally per-
formed through ocean outfall, sewer discharge, evaporation ponds and
deep well injection. Recently, these practices have become untenable
due to environmental risks, constriction of discharge standards and
increase in efforts to recover resources from brine [1–4]. To eliminate
the need for disposal, brine can be treated using the zero liquid dis-
charge (ZLD) approach. ZLD completely avoids the emission of liquid
waste and allows the recovery of water and salts [5]. Sometimes, due to
stringent discharge standards, ZLD is the only way to ensure compliance
with regulations [4]. ZLD can be realized through thermal processes
such as concentrators and crystallizers, which are mature technologies
that have been applied in full-scale plants for many years [4,6]. How-
ever, thermal processes are not economical because they have high
capital investment and consume huge amounts of energy.
The cost of ZLD can be reduced by using a membrane process to
further concentrate brine prior to thermal treatment [4,7] as illustrated
in Fig. 1. Several membrane technologies have been proposed such as
tillation (MD) and forward osmosis (FO) [4,7]. RO is a well-established
process but it can only concentrate brine to salinity of around
70,000 mg/L due to hydraulic pressure limitations [4]. Non-pressure
driven membranes have higher salinity limit than RO and therefore
they can attain higher brine concentration. It has been demonstrated in
pilot-scale studies that MD can reach a brine salinity of 86,000 mg/L
[8], while EDR can reach 100,000–200,000 mg/L [8,9]. Meanwhile, a
recently built ZLD plant has used FO to concentrate industrial brine to a
salinity of 220,000 mg/L [4]. In addition to their high performance,
EDR, MD and FO present opportunities for resource recovery [10], and
therefore they could be attractive options for ZLD. However, the main
challenge that limits membrane efficiency is membrane fouling from
inorganic (also termed “scaling”) and organic matters [11–13]. Scaling
and organic fouling decrease the maximum possible water recovery,
necessitate time and chemicals for membrane cleaning and increase the
frequency of membrane replacement. Scaling can be alleviated through
the addition of acid and antiscalants to the feed [11,12]. Due to the
highly concentrated nature of brine, these approaches are only effective
when the membrane is operated at low water recoveries [14]. Mean-
while, organic fouling is challenging to predict and is dependent on

⁎
Corresponding author at: Sembcorp-NUS Corporate Laboratory, National University of Singapore, Faculty of Engineering, Block E1A, #04-01, 1 Engineering Drive 2, Singapore
117576, Singapore.
E-mail address: ceenghy@nus.edu.sg (H.Y. Ng).

https://doi.org/10.1016/j.desal.2018.04.006
Received 16 January 2018; Received in revised form 10 April 2018; Accepted 13 April 2018
Available online 11 May 2018
0011-9164/ © 2018 Elsevier B.V. All rights reserved.
G.U. Semblante et al.
RO Pre-treatment
brine
Pre-treatment opons:
a) Chemical
precipitaon Membrane opons:
b) Chemical coagulaon i) RO
c) Electrocoagulaon ii) ED/EDR
d) Ion exchange iii) FO
e) Nanofiltraon iv) MD
f) Adsorpon
g) Advanced oxidaon
h) Biological pre-
treatment
Fig. 1. The process flow of a ZLD system with membrane and thermal treatment.
factors such as organic composition and membrane surface character-
istics [15].
To enhance membrane performance in ZLD, a pre-treatment step is
necessary (Fig. 1). The goal of pre-treatment is to remove precursor ions
and potential organic foulants from brine to protect the downstream
membrane processes [16]. By eliminating these compounds, pre-treat-
ment also helps to minimize downstream treatment requirements.
Currently, chemical precipitation is the most common pre-treatment
process in the industry [17]. Although this technique readily reduces
hardness ions (Mg2+ and Ca2+), it is challenging to manage operation
at optimum chemical dosage especially during temporal variation in
brine characteristics. Furthermore, the solid byproduct (chemical
sludge) is considered hazardous and therefore difficult to handle and
dispose [18]. Consequently, there is an ongoing effort to improve the
precipitation process (e.g., through addition of seed material to accel-
erate crystal growth) or to find alternative approaches, which may in-
clude combinations of various technologies.
This review critically analyses the brine pre-treatment technologies
that can be used to achieve ZLD. The performance, cost and limitations
of technologies currently in use are discussed. Other technologies that
might be able to handle the extreme characteristics of brine (e.g., re-
latively high salt and organic concentration) are identified. The po-
tential technologies proposed here are not new; some have been used in
wastewater treatment or as membrane pre-treatment. However, they
are hardly applied specifically for ZLD systems. Successful brine pre-
treatment could enhance the water recovery of membrane processes
and reduce the operating cost of the ZLD process.
2. Challenges in brine management
To determine the removal requirements and to conceptualize an
appropriate pre-treatment strategy, brine analysis must be performed
(Table 1). Brines from brackish or seawater desalination are char-
acterized with relatively high total dissolved solids (TDS), e.g.,
20,000 mg/L [19], and low total organic carbon (TOC), e.g., 2 mg/L
[20]. In comparison, municipal brines have relatively low TDS and high
TOC, e.g., 1000 mg/L and 20 mg/L, respectively [21]. Industrial brines
have a wide range of characteristics based on the source (Table 1). For
example, remarkably high TOC of 200 mg/L has been reported for brine
produced by the tanning industry [22].
Desalination 441 (2018) 96–111
Concentrate
Water Evaporator Crystallizer
recovery
Water reuse
2.1. Potential targets for removal
The key targets for removal during brine pre-treatment are scaling
precursors in the form of divalent ions and organic compounds. The
commonly observed scale-forming compounds include calcium carbo-
nate (CaCO3), calcium sulfate (CaSO4) and silica (SiO2) [11,13], given
the abundance of precursor ions in many types of source waters
(Table 1). The precipitation of CaCO3 can be prevented by removing
alkalinity through acid addition. However, the cost can be significant
especially if the alkalinity is high. Also, this approach is unable to
manage non‑carbonate precipitates that can lead to severe scaling is-
sues. For example, at pH < 7, silica occurs as silicic acid (H2SO3)n that
can aggregate and deposit on the membrane surface [13]. Mono-silicic
acid can also bind on the membrane surface and polymerise to form an
amorphous fouling layer [13]. At pH > 7, silica occurs as silicate ion
(SiO32−)n and reacts with Al3+ and Fe3+ to form metal silicate scale
[13,30,31]. Therefore the relevant precursor ions must be addressed
during the pre-treatment process [32].
The scope of treatment for organic compounds depends on the type
of membrane in the ZLD system. Certain membrane processes are
highly susceptible to membrane fouling. For example, for EDR,
Vermaas et al. [33] reported that 10–20 mg/L of TOC in the feed can
result in fouling and 40% decrease in power density (caused by increase
in pressure drop between inlet and outlet of feed). Nonetheless, using
TOC or dissolved organic carbon (DOC) values is insufficient to predict
fouling potential in membranes since the organic composition may vary
significantly. Brines may contain natural organic matter (NOM), which
consists of humic and fulvic acids and their byproducts [34]. Municipal
and industrial brines originating from biological treatment processes
may also have microbes and microbial byproducts in the form of pro-
teins and carbohydrates [35]. They may further contain refractory
compounds such as pesticides, pharmaceuticals and steroid hormones,
which are ubiquitous in municipal and certain industrial wastewaters,
e.g., agricultural waste [15,35]. Specific types of compounds can be
relevant to fouling. For instance, humic acids would deposit on poly-
amide membrane surface [36]. To date, there is limited information on
the organic composition of brines, especially those produced in in-
dustrial processes, and its impact on membrane fouling in ZLD systems.
97
G.U. Semblante et al. Desalination 441 (2018) 96–111

2.2. Residual ansticalants in brine

wastewater [29]
Commercial antiscalants are solutions made up of phosphonate,

Not reported
Not reported
Not reported

Not reported

Not reported
Not reported

Not reported
Not reported
3380–4550
Municipal

999–1480

800–1000
acrylic acid or phosphonate-acrylic acid blends [37] that are added to

31–49
the upstream RO feed at a dosage recommended by the supplier to
prevent precipitation. They inhibit crystal growth and impart negative
charge in colloidal particles to maintain dispersion [38]. Owing to their
wastewater [21,28]

high chemical stability, they accumulate in the brine at the same con-
centration factor as the RO process. Residual antiscalants may pro-
Not reported
Not reported

Not reported
Not reported
Seawater [19] Seawater [27] Municipal

foundly impact brine treatment in ZLD. They keep brine in a super-

saturated state, i.e., brine could contain more dissolved solids than
1276

159
226
333
7.5
64
12

25
expected under normal conditions [39], which may pose additional
challenge in predicting the precipitation of salts. Moreover, residual
Not reported
Not reported
Not reported
Not reported
Not reported
antiscalants may inhibit brine pre-treatment by chemical precipitation
(discussed in more detail in Section 3.1.3). For example, it was reported
1540
2248
8946

that the efficiency of Ca2+ removal by lime addition was decreased by

368
282
NR
NR

90% due to the occurrence of 85 mg/L of phosphonate-based anti-

scalant in brine [37]. Despite of these drawbacks, residual anticalants
Not reported
Not reported
Not reported
Not reported
Not reported
Not reported

can potentially help prevent scaling in the downstream membrane

21,414

17,431

processes. This may reduce dosing requirement for fresh antiscalants

225
984
7.8

NR

and result in significant savings in chemical cost. A systematic analysis

on the impact of residual antiscalants in different pre-treatment and
Not reported
Not reported

Not reported
Not reported
water [26]

membrane processes will be useful to facilitate ZLD design and opera-

Aquifer

tion.
2190

1118
562

179
7.8

NR
76

13

2.3. Temporal variation in brine characteristics

wastewater [22]

Temporal changes in the feed characteristics, flow rate and day-to-

Not reported

Not reported
Not reported

Not reported

day operation of the upstream processes would lead to fluctuations in

Tannery

15,240

brine concentration and composition. This is particularly true for brine

1124

3020

9996

220

250
6.4

14

generated from a mixture of different industrial sources. The impact of

brine fluctuations on the whole ZLD process is potentially significant.
Agricultural drainage

For example, a change in brine pH from neutral to basic is expected to

facilitate the precipitation of CaCO3 and other scale-forming com-
Not reported
Not reported
Not reported

pounds. To safeguard the downstream membrane processes, it is im-

water [26]

perative that the pre-treatment process is designed to handle the po-

29,960

6360
1232
1060
462
284

260

tential range of variation without compromising product quality.

7.8

31

3. Pre-treatment technologies
wastewater [24]

Not reported

Not reported
Not reported
Not reported
Not reported

3.1. Chemical precipitation

47,000

16,500
Textile

1650
2750

6700
520
8.8

3.1.1. Conventional chemical precipitation

The addition of alkaline solution such as lime (Ca(OH)2), soda ash
Coal seam gas

Not reported

Not reported
Not reported
Not reported

(NaHCO3) or caustic soda (NaOH) (Table 2) is the conventional ap-

water [8]

proach to reduce hardness of supersaturated solutions [7,17,40]. It is

14,100

6840
5520
4740

essential to supply sufficient amount of chemical to promote dissocia-

8.2
14
17

75

tion of bicarbonate (HCO3−) to carbonate (CO32−), which reacts with

Ca2+ to precipitate as CaCO3 when the solubility constant is exceeded.
Magnesium hydroxide (Mg(OH)2) is precipitated via displacement re-
wastewater [23]

action. The resulting solids, termed “sludge,” remove silica and organic
Characteristics of RO brines from different sources.
Petrochemical

Not reported

Not reported
Not reported
Not reported

compounds concurrently by adsorption [32]. However, the mechanism

and kinetics of adsorption have not been fully elucidated.
94–109
26–30
2149

Thus far, chemical precipitation is indispensable to ZLD. A pilot-

134

501

783
7.8

71

scale ZLD system showed that adding NaOH to the brine of primary RO
HCO3− (mg/L)

(operating at 83–90% recovery) resulted in high removal of Ca2+

SO42− (mg/L)
Mg2+ (mg/L)
Ca2+ (mg/L)

DOC (mg/L)
COD (mg/L)
Na+ (mg/L)

SiO2 (mg/L)
TOC (mg/L)
Brine characteristics TDS (mg/L)

Cl− (mg/L)

(> 94%), Ba2+ (> 97%) and Sr2+ (> 88%), moderate removal of
Mg2+ (38–80%) and SiO2 (67–85%) and minor removal of DOC
(11–42%) [32]. The softened brine was subsequently sent to a sec-
pH

ondary RO, which achieved 80% water recovery with antiscalant ad-
dition. By precipitating Ca2+ out of the brine, the system was able to
attain up to 95% water recovery [32]. It is critical to optimize the re-
agent type, reagent dosage and pH based on specific brine character-
istics to avoid process failure. For example, Rahardianto et al. [17]
Table 1

Source

found that NaOH favored the precipitation of salts in the Ca2+-rich

river water RO brine more than lime or soda ash. With respect to pH,

98
G.U. Semblante et al. Desalination 441 (2018) 96–111

Table 2
Application of chemical precipitation process for the treatment of RO brine from various sources.
Source Operating Treatment sequence Alkaline Seed; dosage Removal efficiency Impact on membrane treatment Reference
scale solution;
final pH

Seawater RO brine Jar tests Not applicable Na2CO3 None 67–96% removal at Not applicable [41]
pH 9.8–10.6
Brackish water RO Jar tests Not applicable NaOH Condition #1: Condition #1: 92–93% Not applicable [17]
brine CaCO3; Ca2+ removal
5–12.5 g/L 28% Mg2+ removal
Condition #2: 7–10% SO42− removal
CaSO4; Condition #2: 28% Ca2+
5–12.5 g/L removal
25% Mg2+ removal
No SO42− removal
Lab-scale Primary RO → seeded NaOH; 10.5 CaCO3; 10 g/L 92% Ca2+ removal Primary RO had 90% recovery; [12]
reactor chemical precipitation → 11% Mg2+ removal seeded chemical precipitation
secondary RO 96% Ba2+ removal enabled the secondary RO to have
78% Sr2+ removal 80% recovery (with acid and
17% SiO2 removal antiscalant addition); overall system
15% TOC removal recovery was 98%.
Pilot-scale Primary RO → chemical NaOH; 10 None > 94% Ca2+ removal Primary RO had 90% recovery; [32]
reactor precipitation → secondary > 97% Ba2+ removal chemical precipitation enabled the
RO > 88% Sr2+ removal secondary RO to have up to 80%
38% Mg2+ removal recovery; overall system recovery
67% SiO2 removal was up to 95%.
11% DOC removal
Acid drainage Jar tests Lime precipitation → Ca(OH)2 CaSO4; 4 g/L Ca(OH)2 dosing caused Not applicable [25]
water RO seeded chemical 76–79% Ca2+ removal; it
brine precipitation also removed antiscalants
(3 mg/L) in brine by
adsorption.
CaSO4 seeding caused
rapid particle aggregation.
Municipal Jar tests Not applicable NaOH; 9.5 CaCO3; 90% Ca2+ removal Not applicable [38]
wastewater 0–10 g/L
RO brine Pilot-scale RO → seeded chemical NaOH; 10 CaHPO4; 90% Ca2+ removal The recirculation of treated brine [42]
reactor precipitation → ceramic 1.1–4 g/L resulted in 8% decrease in RO flux;
ultrafiltration → nonetheless, this treatment strategy
recirculate to RO can decrease the cost of brine
evaporation.

Gabelich et al. [32] observed that adjusting pH to 9 only prevented
CaSO4, BaSO4 and SrSO4 scaling in the downstream RO. To avoid
scaling due to silica, pH must be further adjusted to 10.5–11.5.
3.1.2. Seeded chemical precipitation
To enhance the precipitation process, “seed” materials can be added
to provide additional surface area for crystal growth [17,25,42]. Po-
tential seed materials such as CaCO3 [17,25,43], CaSO4 [17,25] and
CaHPO4 [42,44] have been evaluated using synthetic and real water
samples (Table 2). According to literature, hardness removal efficiency
is largely dependent on the seed type and brine composition. For ex-
ample, Rahardianto et al. [17] found that CaCO3 seeding resulted in
better Ca2+ and Mg2+ removal than CaSO4 seeding. This was probably
because the molar ratio (1:1) of Ca2+ and CO32– in their sample was
conducive to CaCO3 precipitation. Sanciolo et al. [42,44] found that
CaCO3 seeding was most effective if there were relatively low con-
centrations of Mg2+, CO32– and PO43 in the sample, whereas CaHPO4
seeding was most effective if there were high concentrations of Mg2+
and CO32−. They further highlighted that CaCO3 seeding was a poor
choice if the sample contains phosphate (e.g., as low as 0.6 mM), which
preferably forms CaHPO4 that adsorbs on CaCO3 surface [44].
The patented slurry precipitation and recycle RO (SPARRO) process
involves the use of gypsum crystals to remove scaling compounds in-
cluding calcium salts and silica. The feed to SPARRO is mixed with
recycled concentrate containing a slurry of crystals, and then passed
through tubular RO system. The RO concentrate is passed through a
cyclone separator to separate the crystals, which are mixed again with
the feed. SPARRO can achieve > 90% water recovery but the system
may have high operating cost due to chemicals and large footprint
[45,46]. Other studies have demonstrated the benefits of seeded che-
mical precipitation in brine treatment. Rahardianto et al. [17] in-
tegrated CaCO3-seeded precipitation in a lab-scale two-stage RO
system. The water recovery of this system (98%) was higher than that of
a similar system [32] with non-seeded precipitation (95%). Sanciolo
et al. [42] treated RO brine by CaHPO4-seeded precipitation followed
by ceramic ultrafiltration, and then recirculated the treated stream to
the RO feed. Although recirculation increased the feed concentration
and caused a slight decrease in the RO flux, this strategy demonstrated
the potential to eliminate costs associated with brine management (e.g.,
evaporation ponds). Given these promising results, it is interesting to
further explore the application of seeded chemical precipitation in ZLD
process. Specifically, a systematic comparison of the reaction kinetics,
removal efficiency and cost of seeded and non-seeded precipitation
should be investigated.
3.1.3. Cost evaluation and other considerations in chemical precipitation
Chemical precipitation using lime or other alkaline solutions can
eliminate scaling of the downstream membrane from calcium pre-
cipitates [17,32]. However, it is not as effective in managing silica and
organic compounds [32]. This is probably because removal of these
compounds by means of adsorption is limited by low surface area of
sludge, electrostatic repulsion and competition for adsorption sites. The
interfacial dynamics are also poorly understood and therefore the
process is difficult to control. Hence, if the brine has high silica or or-
ganic concentration, it is recommended that chemical precipitation is
replaced or combined with another pre-treatment technology that tar-
gets these compounds. For example, silica could be precipitated using
aluminum salts [47] while organic compounds can be removed using

99
G.U. Semblante et al.
coagulation processes (discussed in more detail in Sections 3.2 and 3.3).
This will incur additional capital and operating costs of the ZLD pro-
cess.
One drawback of the chemical precipitation process is high oper-
ating cost due to chemical usage and sludge disposal. Juby et al. [48]
estimated that a lime softening process that receives 4546 m3/d (1
MGD) of RO brine (Ca2+ = 330 mg/L; Mg2+ = 280 mg/L) has an an-
nual operating cost of 0.6 USD/m3 [48]. The type of chemical has sig-
nificant impact on cost. For instance, NaOH (300–400 USD/ton) is more
expensive than lime (80–150 USD/ton) and soda ash (150–250 USD/
ton). Depending on the feed, the sludge byproduct may be tagged as
hazardous waste. The handling and disposal of hazardous waste by
landfilling or incineration may incur considerable expenses. To opti-
mize the process, future research must focus on minimizing the che-
mical consumption or sludge production. It is also worthwhile to ex-
plore other pre-treatment options that offer greater economy.
Another disadvantage of the chemical precipitation process is sen-
sitivity to temporal variations in brine characteristics. The success of
treatment depends on supplying the optimum reagent and reagent do-
sage to induce precipitation. If brine composition and concentration
were to change, the stoichiometric requirements would need to be
adjusted as well. Therefore, the system must be responsive for rapid
dose adjustment to cater for any fluctuations in brine characteristics for
consistent performance, which can be challenging. Although chemical
precipitation is a widely used technology, there is limited information
in literature regarding strategies on maintaining its performance de-
spite temporal variation in brine quality.
Inhibition of the chemical precipitation process may occur due to
residual antiscalants in brine [25,38,49]. Greenlee et al. [37] showed
evidence that adding 85 mg/L of phosphonate-based antiscalant to
synthetic RO brine reduced Ca2+ removal from 87 to 9% during NaOH
treatment at pH 8. They also found that additional CaCO3 precipitation
only occurred when pH was further increased. McCool et al. [49] ob-
served that increasing the concentration of an acrylic acid-based anti-
scalant (3–12 mg/L) during lime precipitation resulted in a five-fold
decrease in CaCO3 formation within 25 min of observation. The me-
chanisms of inhibition are not fully understood because the chemical
structure of the commercial antiscalants is proprietary. A few studies
explored the possibility of removing antiscalants to increase the effi-
ciency of chemical precipitation. Rahardianto et al. [25] observed that
an acrylic acid-based antiscalant can be eliminated from brackish water
RO brine by adsorption on the surface of CaCO3 salts. Removing the
antiscalant accelerated the subsequent precipitation of CaSO4 [49] and
reduced the chemical requirements of the process [37]. Meanwhile,
Greenlee et al. [3] used ozonation (5–10 mg O3/L for 10 min) to break
down phosphonate-based antiscalants. However, it only increased Ca2+
removal slightly from 80–84% to 87–88% by NaOH-induced pre-
cipitation. Furthermore, Yang et al. [39] removed antiscalants from a
synthetic solution using coagulation and subsequently observed pre-
cipitation of CaSO4. Thus far, these studies (i.e., antiscalant removal by
adsorption, coagulation or ozonation) have been limited to jar tests
[25,39] and lab-scale systems [38]. Further investigation must be per-
formed to substantiate their impact on downstream membrane pro-
cesses and economic benefit.
3.2. Chemical coagulation
Chemical coagulation is a conventional treatment process that in-
volves the addition of coagulant (usually aluminum or iron salts) to
destabilize colloids and promote floc formation. It can remove organic
compounds [50], silica [51] and phosphorous [52], depending on
coagulant dosage and pH. Coagulation has not been evaluated as pre-
treatment in ZLD, but a few studies have explored municipal brine
management using aluminum- and iron-based coagulants [53,54].
Generally, they observed good organic removal using FeCl3. Ho et al.
[53] treated municipal brine (TDS = 1056 mg/L; TOC = 24.3 mg/L;
100
Desalination 441 (2018) 96–111
PO43− = 8.7 mg/L; SiO2 = 38.9 mg/L) using ferric chloride (FeCl3),
polyaluminum chloride (PACl) and aluminum chlorohydrate (ACH).
Under the same dosage of 0.6 mM, FeCl3 outperformed the aluminum-
based coagulants in terms of removing TOC (up to 55%) and PO43− (up
to 99%) at different pH (3–7). Liquid chromatography-organic carbon
detection showed that FeCl3 was especially effective in removing humic
substances, building blocks and neutral low molecular weight organic
compounds. Nonetheless, the maximum silica removal was low either
by FeCl3 (15%) or other coagulants (7–14%) [55] probably because
silica was predominantly in dissolved form (i.e., undissociated silicic
acids, H2(SO3)n) under acidic and neutral condition. Likewise, Dialynas
et al. [54] treated municipal RO brine (DOC = 8.5 mg/L) by coagula-
tion and observed higher DOC removal due to FeCl3 than alum
(Al2(SO4)3), i.e., 69% vs 42%. On the contrary, Ordóñez et al [56] re-
ported PACl was the preferred coagulant applied for treatment of paper
mill industry brine over FeCl3. This was because FeCl3 imparted a dark
red-brown colour to the brine, which affected the product quality.
Nonetheless, PACl addition caused an increase in brine conductivity. To
work around this issue, PACl (dosage = 2000–3000 mg/L) was com-
bined with lime softening, which decreased brine conductivity due to
the precipitation of CaCO3 and Mg(OH)2. Alternatively, PACl was
supplemented with anionic polymer (1–7 mg/L), which attracted Ca2+
and Mg2+ anions and helped to facilitate flocculation. Either strategy
resulted in 30–70% of COD removal depending on coagulant dosage
and operating pH.
Coagulation has also been explored to specifically target anti-
scalants in brine in order to facilitate CaSO4 precipitation. Yang et al.
[39] added either PACl (60–240 mg/L) or SDS (38–300 mg/L) to syn-
thetic brine supersaturated with respect to Ca2+ (3250 mg/L), SO42−
(6300 mg/L), Na+ (6007 mg/L) and Cl− (10,352 mg/L). At the
minimum dosage of 60 mg/L, PACl removed the antiscalants
(10–34 mg/L) that were responsible for keeping the brine in a super-
saturated state. The removal of antiscalant subsequently enabled
spontaneous precipitation of CaSO4. On the contrary, SDS was unable to
remove any of the antiscalants and thus, CaSO4 formation was not
observed.
Thus far, there is no information on the cost of brine treatment by
chemical coagulation. Analysis based on other types of wastewaters has
shown considerable operating cost due to high chemical usage and
sludge disposal. Moosavirad [57] estimated that the cost of treating
mining greywater (COD = 700 mg/L) by PACl, alum or FeCl3 at the
dosage of 100–1200 mg/L was 0.09 USD/m3. Demirbas and Kobya [58]
reported that the cost of metalworking fluid wastewater treatment by
alum (500 mg/L) was 0.12 USD/m3. This included the cost of alum
(0.14 USD/kg), energy (0.13 USD/kWh) and chemical sludge disposal
by landfilling (0.1 USD/kg).
In summary, coagulation is effective at removing organic com-
pounds. However, the disadvantages of coagulation include poor re-
moval of silica under acidic and neutral pH [55], potential to adversely
affect the brine quality and high dosage requirement (e.g., > 2000 mg/
L) [56]. Clearly, pre-treatment using chemical coagulation alone is not
sufficient for brines with high concentrations of hardness or silica. It
might be worthwhile to combine coagulation with another pre-treat-
ment technology, e.g., chemical precipitation [56], to create a sy-
nergistic pre-treatment train. The economic feasibility of this approach
is subject to brine characteristics and chemical cost.
3.3. Electrocoagulation
Electrocoagulation (EC) involves the in-situ generation of coagu-
lants using an electrolytic cell. Upon application of current, polyvalent
cations are liberated from the sacrificial anode while hydrogen gas and
hydroxide ions are produced at the cathode. The cations spontaneously
react with hydroxide ions to form insoluble precipitates that instigate
the coagulation process [59,60]. The potential advantages of EC over
conventional coagulation are: (i) lower sludge production; (ii)
G.U. Semblante et al. Desalination 441 (2018) 96–111

Table 3
Studies investigating scaling and fouling precursor removals by EC process.
Source Operating Scale/ Electrode Target Pollutants: Initial Initial pH Removal Efficiency (%) Reference
Mode Material Concentration (Final pH)
(Electrode (mg/L) 1
Connection)

Seawater Lab-scale/Batch A, C: Al TH2: 6676 8.2 TH: 8 – 13 [63]

(MP, Series) DOC: 1 (4.3) DOC: 70.8
Simulated Oily Polymer-flooding Lab-scale/Batch A, C: Al Ca2+: 301 8.28 COD: 74.9 [64]
Produced Water (BP, Series) Mg2+: 227
COD: Not provided3
Mixed Industrial Wastewater Lab-scale/Batch A, C: Copper TH: 1059 2, 4, 7 TH: 78.0 [65]
(MP) TOC: 1080 TOC: 48.4
COD: 2300 COD: 89.1
Tap Water Lab-scale/Batch A4: Al TH: 355 7.36 TH: 80 [66]
C: SS Ca2+: 255 (8.5 – 11.2)
(MP, Parallel) Mg2+: 100
Drinking Water Lab-scale/Batch A, C: Fe Ca2+: 138 8.35 TH: 95.7 – 98.2 [67]
(MP, Parallel) Mg2+: 162 (~10)
River Water Lab-scale/Batch A, C: Fe Ca2+: 71.3 7.6 TH: 21 [68]
(MP, Series) Mg2+: 41.7
Produced Water (O&G) Lab-scale/ A, C: Fe TH: 287 – 1284 6–7 TH: Up to 85.7 [69]
Continuous (MP, Parallel) TOC: 512 – 2490 TOC: Up to 64
Lab-Generated ROC (Mining Lab-scale A, C: Fe Ca2+: 2494 4 Ca2+: 90 [69]
Groundwater) /Continuous Mg2+: 1111 (115) Mg2+: ~100
SiO2: 220 SiO2: ~100
Synthetic First-Stage BWRO Reject Lab-scale A: Al Ca2+: 499 7 SiO2: Up to 80 [70]
/Continuous C: SS Mg2+: 412
(BP, Series) SiO2: 120
First-Stage BWRO Reject Lab-scale A: Al Ca2+: 409 6.5 – 7.5 SiO2: Up to 80
/Continuous C: SS Mg2+: 535 (6.9 – 7.3)
(BP, Series) SiO2: 83 – 130
ROC (Semiconductor Fabrication Feed) Lab-scale A, C: Al/Fe Ca2+: 87 7.8 – 8.2 Al Fe [71]
/Continuous (MP, Parallel) Mg2+: 49 Ca2+: ~30 Ca2+: 20
SiO2: 65 – 75 Mg2+: ~30 Mg2+: 20
SiO2: 80 SiO2: 70
Pilot/Continuous Ca2+: ~25 Ca2+: 20
Mg2+: ~25 Mg2+: 20
SiO2: ~80 SiO2: ~80
Produced Oil Field Water Pilot/Continuous A: Fe TH: 300 7–8 TH: 85.8 [72]
C: Graphite COD: 280 (6 – 12) COD: 66.6
(MP, Parallel)
Drinking Water Pilot A, C: Al Ca2+: 316 5.3, 7.2, TH: 47 – 95.6 [73]
Mg2+: 148 10.1
Fluorescent Penetrant Liquid Full/Continuous A, C: Al COD: 1000 – 2500 6.5 – 7.5 COD: > 90 [74]
(7 – 7.5)

1
Hardness concentrations given as mg/L CaCO3. All other parameters expressed as mg/L.
2
Total Hardness (TH).
3
Initial COD not reported. Concentration of dissolved polymer, which contributes to COD, was 300 mg/L.
4
A and C refer to the anode and cathode, respectively. Aluminium, Iron and Stainless Steel are denoted as Al, Fe and SS, respectively.
5
pH of concentrate was raised to 11 by NaOH during treatment, and post-treatment pH was reported as 11.

elimination of chemical additives for treatment; and (iii) smaller foot- Table 4
print. The main disadvantages are the periodic replacement of the sa- Summary of reactions and possible precipitation mechanisms for hardness re-
crificial anodes, passivation of cathodes and incomplete understanding moval in EC [63,67,68,72,73].
of underlying reactions responsible for pollutant removal [59,61,62]. A Principal Carbonate generation Possible precipitation
few studies have applied EC specifically for brine treatment and have cathodic reactions
investigated the removal of scaling/fouling precursors (hardness, or- reaction
ganics, silica) in similar treatment contexts (Table 3). Therefore, there
2H2O + 2e− → HCO3− + 2OH− → CO32 − + 2H2 O CO32 − + Ca2 + → CaCO3
is a basis for analyzing the applicability of EC as a pre-treatment H2 + 2OH− CO32 − + Mg2 + → MgCO3
technology for RO brine within a ZLD treatment framework.
SO4 2 − + Ca2 + → CaSO4
OH− + Mg2+ → Mg(OH)2
3.3.1. Performance of electrocoagulation
EC has reportedly achieved > 80% hardness removal from various
media [67,69,73] including brine from mining industry [75]. This
performance, which is at par with chemical precipitation, makes EC an Indeed, several lab-scale studies reported excellent hardness removal by
attractive brine pre-treatment option especially since EC has relatively EC when pH > 9. For instance, Malakootian [67] and Malakootian and
low sludge production. However, the underlying mechanisms of hard- Yousefi [73] observed 95% hardness removal from drinking water at
ness removal in EC are not fully understood. Hardness removal has been pH 10. Esmaeilirad et al. [69] obtained up to 86% hardness removal
attributed to precipitation reactions in the cathode as summarized in from produced water at pH 9.5. The reverse treatment sequence (EC
Table 4 [63,67,68,72,73]. Some of the key reactions (e.g., precipitation followed by alkaline addition) resulted in poorer performance [69],
of CaCO3 and Mg(OH)2) occur spontaneously under alkaline condition. meaning that alkaline condition facilitated the removal mechanism.

101
G.U. Semblante et al.
Subramani et al. [75] observed that increasing pH to 11 resulted in 90%
Ca2+ removal and virtually complete Mg2+ removal. One may argue
that high reaction pH could be the driving force behind hardness re-
moval rather than the EC process itself. However, hardness removal in
EC has also been reported under neutral [72] and acidic conditions
[65]. Zhao et al. [72] observed optimum hardness removal (85.8%) at
an initial pH of 7, in tandem with optimal COD and turbidity removal.
Likewise, Garcia-Garcia et al. [65] obtained high hardness removal
(78%) at an initial pH of 4 possibly due to calcium complex formation.
To optimize the process and elucidate underlying mechanisms, a sys-
tematic investigation on the effect of pH on hardness removal in EC
should be performed.
There is little information on the removal of organic compounds
from brine by EC. Nonetheless, critical information can be drawn from
the application of EC in water/wastewater treatment [61,76–78].
García-García et al. [65] studied a sequential EC and electro-oxidation
process for treating mixed industrial wastewater (COD = 2300 mg/L)
with a high total hardness (1059 mg CaCO3/L). The EC step removed
48% TOC, with an initial pH of 4 and a current density of 96.8 mA/cm2.
In the work done by Esmaeilirad et al. [69] for hydraulic fracturing
produced water (TOC = 512–2490 mg/L), a sequential softening-EC
treatment (Soft-EC) delivered 64% TOC removal, while the reverse
sequence (EC-Soft) achieved 35% TOC removal. Hakizimana et al. [63]
focused on DOC abatement from seawater (DOC0 = 1 mg/L) and at-
tained 70.8% removal at a current density of 22.4 mA/cm2. They also
postulated that the aromatic organic compounds were likely to be re-
moved by EC. Given the broad success of EC in organic pollutant
abatement, further investigation should be performed to determine its
efficacy for niche applications such as ZLD.
Only a few studies have evaluated the removal of silica by EC. Den
and Wang [70] attained up to 80% removal of silica from synthetic and
real brackish water RO brine (SiO2, 0 = 83–130 mg/L) using aluminum
anodes, and attributed the removal performance to the formation of
stable hydroxyaluminosilicates. The work produced by Subramani et al.
[75] showed that EC reduced silica concentrations from a synthetic
mining groundwater ROC (SiO2, 0 = 220 mg/L) to below method de-
tection limits, which was higher than the removals attained by Ca(OH)2
and NaOH softening (81% and 86%, respectively). Schulz et al. [71]
concluded that EC could remove up to 80% of silica from a RO reject
stream with semiconductor fabrication wastewater as its feed (SiO2,
0 = 65–75 mg/L). These results verified the technical feasibility of EC
specifically for silica removal from ROC, which makes it a viable con-
sideration for ZLD pre-treatment.
3.3.2. Cost evaluation and other considerations in electrocoagulation
There is a number of techno-economic analyses of the EC process
reported in the literature. Kobya et al. [79] assessed the cost effec-
tiveness of a bench-scale continuous flow system with aluminum and
iron electrodes to remove COD, TOC and turbidity from textile industry
effluent. The COD removal efficiencies of EC with Al and Fe electrodes
were 77% and 85%, respectively, while the operating costs were
1.85 USD/m3 and 1.56 USD/m3, respectively. Based on the required
cost per unit of COD removed, Fe electrodes were almost twice as cost
efficient as Al electrodes. It is noted that operating cost was based only
on energy, electrode and auxiliary chemical consumption, and the cost
of sludge management was excluded in the calculation. Another study
by Lin et al. [80] investigated the cost of a pilot-scale EC process using
Al electrodes for greywater treatment. For an average COD removal
efficiency of 60%, the normalized overall cost was 0.27 USD/m3.
Electricity and sludge treatment were the major costs components
(25.9% and 22.3% of the cost, respectively). The study also showed that
EC was more cost-effective compared to other treatment options in-
cluding biological oxidation, sand filtration, microfiltration, ultra-
filtration, UV and ozonation.
In summary, EC is an attractive pre-treatment option for ZLD due to
its potential to remove hardness, organic compounds and silica. Under
102
Desalination 441 (2018) 96–111
certain conditions, EC can achieve similar hardness removal but lower
sludge production than chemical precipitation. The major challenge in
EC is the elucidation of the mechanics of hardness removal, which is
critical for process optimization and technology transfer from lab- to
full-scale application. Together with rigorous techno-economic ana-
lyses, more realistic process and cost comparisons with conventional
processes can then be performed for applying EC in a full-scale ZLD
process.
3.4. Ion exchange
Ion exchange involves the replacement of cations in solution for
anions associated within a matrix (e.g., resin) or vice versa [81]. De-
pending on the active functional group, the resin can also capture small
charge-bearing organic compounds such as humic or fulvic acids [82].
Commercial resins have consistent removal efficiency and relatively
low cost. Ion exchange has shown potential as pre-treatment to remove
scaling precursors from seawater, and has been critical to increase the
water recovery of the downstream RO by 20–50% [81,83,84]. Ion ex-
change efficiency is dependent on the type of resin. Generally, four
types of commercial resin are available: strong acid cation (SAC), strong
base anion (SBA), weak acid cation (WAC) and weak base anion (WBA)
[81]. SAC, which commonly bears sulfonic acid groups, has a lower
exchange capacity than WAC, which has carboxylic acid groups. It is
noted that SBA, which typically has tertiary amine groups, has a higher
exchange capacity than WBA, which has quarternary amine groups
[81]. The hardness removal efficiency of the ion exchange process is
affected by the TDS of the solution. These factors are linked because the
exchange is dependent on the availability of monovalent ions in the
resin. The reaction shifts to the left (Eq. (1)) as TDS increases. The
maximum hardness and TDS that resins can handle range from
500–2000 and 5000–30,000 mg/L, respectively. Some resins also per-
form selective sequestration of various compounds such as SiO2, B and F
[81].
CaSO4 + 2Na+ + R ⇄ Ca−R + Na2 SO4 , where R = SAC (1)
High efficiency reverse osmosis (HERO) is a patented process that
involves the treatment of primary RO brine with ion exchange, dega-
sification and acidification followed by secondary RO. The ion ex-
change process involves the use of WAC to remove divalent ions in-
cluding Ca2+. HERO can achieve > 90% water recovery from brackish
water, but operating cost is high due to chemicals and sludge man-
agement [45]. Other studies have investigated the use of ion exchange
in brine management. Pérez-González et al. [85] used lab-scale cationic
and anionic exchange resin columns to eliminate scaling precursors
from brackish water RO brine (TDS = 20,700 mg/L; Ca2+ = 1800 mg/
L; Mg2+ = 1600 mg/L; SO42− = 8500 mg/L). They observed that WAC
resin (Lewatit TP208, Lanxess) preferentially exchanged with Ca2+
over Mg2+. Nonetheless, high removal of both ions (approximately
90% and 80%, respectively) was achieved after eight bed volumes (bed
volume = (flow rate × time) / resin volume). They further used SBA
resin (Lewatit Monoplus M600, Lanxess) to target SO42−, but observed
that the resin was completely saturated at less than one bed volume.
This means that it had a low exchange capacity for SO42−. Venkatesan
and Wankat [86] simulated the use of SAC resin (Dowex Marathon C10,
Dow) to treat brackish water primary RO brine (Ca2+ = 95 mg/L;
Mg2+ = 35 mg/L; Ba2+ = 0.1 mg/L). They predicted that ion exchange
can achieve high removal of Mg2+ (97%), Ca2+ (99.9%) and Ba2+
(99.9%). However, it is unable to capture silica, thus the secondary RO
can only be operated at 63% recovery due to silica precipitation. Fur-
ther treatment of secondary RO brine with acid (adjustment to pH 6
using HCl) and heat (35–45 °C) prior to tertiary RO treatment was
predicted to increase the overall system recovery to 95%.
The efficiency of ion exchange can be hampered by competition
amongst various ions. For example, Pérez-González et al. [85] found
that Lewatit Monoplus M600 (Lanxess) had greater affinity for NO3−
G.U. Semblante et al.
than SO42−. This is problematic because removing SO42−, which causes
scaling in downstream membranes, is of higher priority than removing
NO3−. Acevedo et al. [87] reported that the actual silica removal (6%)
from synthetic brine using SBA resin (Dowex 21 KLXT, Dow) was far
lower than the theoretical value (73%), which could be due to the
adsorption of other anions. The issue was worsened by the undesirable
formation of Ca(OH)2 and Mg(OH)2 that caused pore plugging [87].
The removal efficiency might be increased by exploring other types
of resins. Furthermore, the scope of treatment might be enhanced by
using multiple resins to target specific compounds at the same time
[88]. Apell and Boyer [88] tested this strategy for groundwater re-
mediation, and found that commercial anionic and ionic resins (Orica
Watercare) simultaneously removed 70% of dissolved organic matter
and 55% of hardness in a completely mixed reactor. It would be ad-
vantageous if a similar approach could be adapted for brine pre-treat-
ment so that inorganic and organic foulants can be addressed in a single
step.
It has been reported that the typical operating cost of an ion ex-
change system is 0.08–0.21 USD/m3, primarily attributed to the cost of
regeneration chemicals [81]. To reduce the operating cost, the re-
cycling of RO brine as a regenerant in place of fresh solution has been
explored [83,84]. The feasibility of this approach has been demon-
strated in a pilot-scale system that treated brackish water using hybrid
ion exchange (Lewatit C249, Lanxess) and RO (LC HR, Dow) [84]. It
was found that regeneration efficiency increased as the ratio of
monovalent ions (Na+ and K+) over polyvalent ions (Ca2+ and Mg2+)
in the brine increased. At the ratio of 25 (i.e., when the concentration of
monovalent ions was 25 times greater than that of polyvalent ions),
fresh NaCl addition was reduced from 60,000 to 250 mg/L [84]. It will
be interesting to apply this strategy to minimize the cost of brine
management in ZLD. The downstream membrane in ZLD is expected to
produce a high saline reject stream that is a good candidate as a re-
generant. Nonetheless, brine quality differs depending on feed char-
acteristics and membrane operating conditions. Therefore, the effec-
tiveness of a certain reject stream as a regenerant must be evaluated on
a case-by-case basis.
3.5. Nanofiltration
NF membranes have pore size and performance level that are be-
tween ultrafiltration (UF) and RO membranes [55]. They are marked by
high rejection of polyvalent ions and low to moderate rejection of
monovalent ions and small organic compounds [55,99]. Compared to
RO, NF has higher flux, lower energy consumption and longer mem-
brane life [89]. Because of this, NF has been integrated in membrane-
based desalination to decrease membrane fouling and increase water
recovery, as well as in thermal-based desalination to decrease reactor
scaling and thermal efficiency [55].
NF has been previously applied in brine management (Table 5). For
instance, a patent has been applied for combined lime softening and NF
for treatment of industrial RO brine with TDS > 2000 mg/L and
COD > 200 mg/L [90]. A patent has been granted for brine treatment
using combined NF and electrodeionization (ED), a separation tech-
nique that uses both ion-exchange resins and membranes for water
purification [91]. Recently, NF has been used as pre-treatment for ED;
Liu et al. [92] used NF-ED treatment for seawater desalination brine
with high hardness and TDS (Table 4). In that study, NF (DL, GE) was
operated at low recovery (25–50%) to remove SO42− (99%), Ca2+
(40%) and Mg2+ (87%). The NF reject was used as the concentrating
solution of ED. Almasri et al. [93] used chemical precipitation-NF-RO to
treat brackish water RO brine. The NF reject generated from this pro-
cess was treated by two-step addition of (1) calcium chloride (CaCl2) to
precipitate CaSO4, and (2) NaAlO2 + Ca(OH)2 to precipitate calcium
sulfoaluminate (Ca6Al2(SO4)3(OH)12). By further concentrating the
brine, lesser amount of chemicals was required for SO42− removal.
The capital costs of membrane processes are associated with
103
Desalination 441 (2018) 96–111
membrane elements, pressure vessels, pumps, valves and instrumenta-
tion. The capital cost could be high, e.g., 17 USD for a drinking water
plant with a capacity of 100,000 m3/d [96]. Generally, greater
economy will be achieved when the system is operated at higher water
recovery. For example, it has been reported that the operating cost of
surface water treatment by NF targeted to operate at 83% recovery
(0.08–0.09 USD/m3) was remarkably lower than that of the same
system operating at 68% (0.10–0.11 USD/m3) [97]. This is because
greater volume of product is generated with the same energy con-
sumption. However, other factors (e.g., cleaning chemicals and fre-
quency) must be considered to accurately measure the operating cost
because these impact membrane replacement [97].
The available literature suggests that NF has a high potential to
eliminate scaling precursors from brine [2,92,93]. Nevertheless, it is
necessary to address several knowledge gaps regarding NF. Firstly,
there is lack of data on organic fouling in NF during brine filtration.
This is an important consideration because fouling will limit the max-
imum recovery in the downstream membrane process. Secondly, the
impacts of NF on the performance and fouling of the downstream
membrane processes have yet to be addressed satisfactorily, limiting
the decision in selecting NF as the preferred pre-treatment technology
over other available technologies. To date, only Khedr [94] showed a
systematic comparison of NF and another technology (lime softening)
as potential pre-treatment, which revealed that NF can remove a wider
range of ions than lime softening, leading to a decrease in TDS. Thirdly,
the current results are limited to lab-scale systems, which yields little
information regarding operational cost and long-term system perfor-
mance. Pilot-scale testing is an essential step to determine the potential
of NF as a pre-treatment process in ZLD.
3.6. Adsorption
Adsorption is a widely used technology in wastewater treatment for
the removal of refractory organic compounds, heavy metals, nutrients
and other pollutants [98]. Activated carbon in the form of powdered
activated carbon (PAC) and granular activated carbon (GAC) is the
most commonly used adsorbent in the industry due to its high surface
area and porosity resulting in excellent adsorption capacity [98]. The
main disadvantage of this process is high cost due to the need for
continuous dosing or regeneration of adsorbent due to finite adsorption
capacity [52]. The removal of organic compounds from brine using
activated carbon has been investigated in lab-scale studies [15,54].
Zhou et al. [15] reported high removal of DOC by GAC (88%) and PAC
(95%) from municipal RO brine (DOC = 18 mg/L) at the dosage of
5 mg/L. The small fraction of DOC that were not adsorbed were hy-
drophilic and have high molecular weight [15]. Similarly, Dialynas
et al. [54] reported high DOC removal (91.3%) from municipal RO
brine (DOC = 10 mg/L) using 5 mg/L of GAC. It is noted that micro-
organisms have been immobilized on activated carbon to form a system
called biological activated carbon (BAC), which integrates adsorption
and biological treatment in one process. The application of BAC in brine
management is discussed in more detail in Section 3.8.2.
Brine treatment with adsorbents other than activated carbon has
hardly been investigated. A recent lab-scale study by Lin et al. [99]
investigated the use of biochar, a type of charcoal derived from plant
matter, for the removal of refractory compounds from RO brine
(TDS = 6500 mg/L; Mg2+ = 155 mg/L; Ca2+ = 179 mg/L). They
found that biochar and commercial GAC had comparable adsorption
capacity for the refractory compounds (i.e., ibuprofen and sulfa-
methoxazole), which makes biochar a promising low-cost adsorbent.
The use of biochar and other recycled materials as adsorbent has po-
tential to decrease operating costs, and therefore it is interesting to
determine if they can be applied in brine management.
There is contention in literature regarding the impact of inorganic
constituents in brine on DOC adsorption. On one hand, inorganic con-
stituents can hinder organic adsorption by competing for adsorption
 G.U. Semblante et al.

Table 5
Application of NF process in RO brine treatment.
Source Operating Treatment sequence Brine properties (mg/L unless NF operation and performance NF fouling Downstream treatment Reference
scale specified otherwise)

Not specified Not specified RO → lime softening → TDS > 2000 1. Na2CO3 was added to adjust to CaSO4 caused Not reported Patent WO 2014089796
MF → NF COD > 100 pH 10–11 to precipitate sulfate. scaling A1, GE Co. [90]
2. MF was used to separate solids.
3. NF was operated at 95–98%
recovery.
Not specified Not specified RO → NF → EDI Not reported Not reported Not reported EDI produced pure water (0.055 μS/cm). Patent 7470366 B2, GE
The entire system consumed < 2 MJ/m3 pure Mobile Water Inc. [91]
water.
Bacteria formed in EDI unit and caused fouling.
Not specified Lab-scale 1st stage RO → NF → 2nd TDS = 17,000 NF was operated at 40% recovery N not NF increased the recovery of the 2nd stage RO [94]

104
stage RO Ca2+ = 2000 reported from 52% to 63%
Mg2+ = 600
SO42− = 3000
Na+ = 3000
Seawater Lab-scale RO → NF → ED TDS = 44,500–88,000 NF (DL2540, GE) was operated at Not reported ED (stack voltage = 15 V) produced a [92]
Ca2+ = 520–840 25–50% recovery with flux of 30–55 concentrated stream with NaCl = 160,000 mg/
Mg2+ = 1650–3430 LMH L.
SO42− = 3470–6790
Na+ = 13,600–6790
Brackish water Lab-scale 1. 1st stage RO → lime Not reported Not reported Not reported Treatment of NF brine: [93]
softening → NF → 2nd stage 1st step: addition of CaCl2 to form CaSO4
RO 2nd step: addition of NaAlO2 + Ca(OH)2 to
2. NF brine → chemical form calcium sulfoaluminate
precipitation (Ca6Al2(SO4)3(OH)12)
Coal seam gas Lab-scale 1st stage RO → NF → 2nd Data not shown Coagulation using aluminum Not reported Not reported [95]
water stage RO chlorohydrate removed 70.5% of
dissolved silica
Desalination 441 (2018) 96–111
G.U. Semblante et al.
sites. The negative impact of hardness (e.g., 80–200 mg/L as CaCO3)
has been observed in the adsorption of a specific organic compound
(e.g., caffeine) on activated carbon [100]. On the other hand, ions can
enhance organic adsorption by increasing the ionic strength of the so-
lution. When ionic strength is sufficiently high, it can neutralize a ne-
gatively-charged adsorbent [101]. Consequently, this reduces the re-
pulsion between negatively-charged organic compounds and adsorbent
surface. Increasing ionic charge has led to an increase in the adsorption
of small organic compounds (e.g., ibuprofen and sulfamethoxazole) on
activated carbon [99].
The available literature suggests that activated carbon could be used
to remove organic compounds in brine. However, the removal effi-
ciency can be affected by several factors – inorganic composition and
concentration, type and surface charge of the adsorbent and interac-
tions of various solutes with the surface of the adsorbent. If adsorption
process were to be applied as pre-treatment, it must be coupled with
another technology that can address hardness and silica removal.
3.7. Advanced oxidation
Advanced oxidation processes (AOPs) involves the use of hydroxyl
radicals (%OH) to break down organic matter. The radicals are gener-
ated in situ by treatment with ozonation, UV/H2O2 or photocatalysis. In
brine management, research on AOPs has largely focused on its appli-
cation to remove micropollutants (< 5 μg/L) from municipal samples
[102]. Research has shown that ozonation at a sufficient dose (e.g.,
10 mg O3/L) could completely remove a wide range of micropollutants
including antibiotics, analgesics and beta blockers, amongst others
[102]. UV/H2O2 could potentially be an alternative to ozonation be-
cause it requires a lower amount of oxidant (e.g., 1.4 mg O3/g TOC vs.
0.5 mg H2O2/g TOC) to achieve the same removal performance [103].
Although AOPs generally have high oxidizing power, their overall
performance is negatively impacted by other constituents of brine such
as dissolved organic matter and alkalinity. It has been found that ozo-
nation efficiency decreased at high brine DOC (e.g., 46 mg/L) possibly
due to competition with natural organic matter for ozone and hydroxyl
radicals [102]. It has been noted that TiO2 photocatalysts did not
achieve high removal of micropollutants due to adsorption with humic
acids [104]. The photocatalytic surface area of TiO2 was further re-
duced due to agglomeration with Ca2+ [104].
AOPs could only address the organic components of brine. The cost
of equipment and energy requirements of AOPs are generally high. For
example, Huysmans et al. [105] projected that the cost of ozone in-
stallation and production was 3.75 EUR or 4.20 USD per kg of O3
produced (1 EUR = 1.12 USD as of 2016). Given the high cost of pro-
ducing the oxidants, less expensive technologies such as biological
processes must be considered as potential pre-treatment in ZLD.
3.8. Biological pre-treatment
3.8.1. Activated sludge
The activated sludge process has high biotransformation efficiency
at relatively low capital and operating cost. Activated sludge has been
studied for nitrogen and sulfate removal from brines. Since brines
generally do not have high biodegradable content, an external carbon
source was supplied to sustain the biomass. For instance, Ersever et al.
[29] performed batch nitrification studies using municipal RO as the
feed and ethanol as the external carbon source. They found that bio-
logical denitrification reaction occurred, and ammonia in the brine was
reduced from 62 to 98 mg/L to 1 mg/L (up to 99% removal). The op-
timum denitrification occurred at the temperature of 35 °C, pH of 8,
TDS of 4000 mg/L and C:N ratio of 1.5. Recently, Li et al. [106] used a
lab-scale sequencing batch reactor supplemented with sodium acetate
to treat coking wastewater RO brine. They found that the bioreactor
reduced TN from 200 to 19 mg/L (90% removal) and NO3− from 170 to
11 mg/L (94% removal). These effluent concentrations were below the
105
Desalination 441 (2018) 96–111
Chinese national discharge standards. Jung et al. [14] assessed sulfate
reduction from municipal RO brine using a lab-scale fluidized bed re-
actor. They found that the biological conversion of sulfate to sulfide was
favorable under anaerobic condition with either ethanol or acetate as
an external carbon source. In that study, the biological process was used
as pre-treatment to facilitate downstream RO. The effluent of the FBBR
was acidified and sparged to strip hydrogen sulfide (H2S) before passing
through a secondary RO process to recover 70% water with low TDS.
3.8.2. Biological activated carbon
Biological activated carbon (BAC) has been applied to remove or-
ganic compounds from municipal RO brine [28,107,108]. The removal
mechanism in BAC is adsorption followed by biodegradation by mi-
croorganisms attached on the activated carbon. The reported organic
removal efficiency of BAC had been low, e.g., 28% DOC removal [107]
and 16–23% TOC removal [28]. This was possibly due to the low ad-
sorption capacity or poor biodegradability of the organic components.
To improve the process performance, BAC has been combined with AOP
[21,108] or physicochemical treatment [28]. Lu et al. [108] reported
that pre-oxidation of brine by UV/H2O2 increased the DOC removal of
BAC from 39 to 59%. The pre-oxidation step involved dosing with 4 mM
H2O2 and UV irradiation for 30 min. Lee et al. [21] showed that pre-
ozonation of brine at 6 mg O3/L for 20 min increased the TOC removal
of BAC from 23 to 70%. The AOPs helped to break down refractory
organics such as aromatic and humic substances into smaller molecules
that were more readily adsorbed and biodegraded in BAC [21,108].
Another strategy was to further treat BAC effluent with acid addition
(adjustment to pH 6.5 using 0.1 N HCl) and ultrafiltration, which led to
an overall TOC removal of 49% [28]. This combined biological and
physicochemical pre-treatment enabled a downstream capacitive
deionisation (CDI) process to operate for 36 h without pressure build up
(due to fouling). In contrast, BAC alone prevented pressure build up in
the CDI for 18 h only. In other words, the combined pre-treatment can
reduce fouling in the downstream CDI by at least 50% [28].
Cost analysis of UV/H2O2-BAC and ozonation-BAC treatment for RO
brine has been performed [109]. The capital and annual operating cost
of a UV/H2O2 system receiving 37,854 m3/d (10 MGD) of feed water
were estimated to be 111 USD/m3 and 7.9 USD/m3, respectively. It is
further noted that of ozonation receiving the same feed was 187 USD/
m3 and 5.3 USD/m3, respectively. Coupling these technologies to BAC
(269 US/m3 and 2.6 USD/m3, respectively) results in a very high
treatment cost that might not be viable for brine management.
3.8.3. Microbial fuel cell
A microbial fuel cell is a bio-electrochemical system that drives an
electric current by using microorganisms. Luo et al. [110] proposed to
treat RO brine using a microbial fuel cell that simultaneously performed
desalination and acid/base production. The cell had four chambers that
were separated by bipolar membrane (between biotic anode and acid
production chamber), anion exchange membrane (between acid pro-
duction and desalination chamber) and cation exchange membrane
(between desalination and cathode chamber). The microorganisms in
the anode served as biocatalyst for redox reactions. During operation,
negatively- and positively-charged ions from the brine migrated to the
acid production and cathode chambers, respectively. After 18 h of op-
eration, the TDS of the brine decreased from 2684 to 575 mg/L (79%
reduction). Also, from an initial pH of 6.7, the final pH of the acid
production and cathode chambers became 1.5 and 11.6, respectively.
Although the process had low energy consumption, the maximum
current density in the proposed system (10 A/m2) was significantly
lower than that of mature processes such as ED (500 A/m2). This means
that ion transfer efficiency was very low. This is a major issue that must
be overcome if bioelectrochemical processes were to be applied in brine
management.
 G.U. Semblante et al.

Table 6
Application of biological pre-treatment processes in RO brine treatment.
Biological pre- Source Scale Operation conditions Performance Impact on downstream membrane process Reference
treatment

Activated sludge Municipal RO brine Batch tests Batch experiments were performed using with ethanol as the 99% NH4+ removal Not evaluated [29]
external carbon source.
−
Coking wastewater Lab-scale The denitrification reactor had sludge retention of 20 d and mixed 99% TN removal; 90% NO3 Not evaluated [106]
RO brine liquor suspended solids of 3800 mg/L. Sodium acetate was added as removal
the external carbon source to achieve feed C:N ratio of 8:1.
Municipal RO brine Lab-scale Biological sulfate reduction was performed in a fluidized bed Not reported Biological pre-treatment enabled the secondary RO to [14]
reactor. Ethanol was added as the external carbon source. The operate at 70% recovery.
effluent was subsequently acidified and sparged to strip H2S and
CO2. The biological sludge was removed through filtration. The
effluent was further treated using secondary RO process.
Biological activated Municipal RO brine Lab-scale Three pre-treatment methods were performed: (1) BAC column 1. BAC only: 16% TOC removal The pre-treatment enabled the downstream CDI to [28]
carbon (BAC) packed with GAC and with EBCT of 60 min; (2) using the same BAC 2. BAC with acid addition: 24% have 85% recovery; BAC with acid addition
column followed by acidification of the BAC effluent to pH 6.5 with TOC removal significantly reduced CDI fouling (~50%).
HCl; (3) using the same BAC column followed by acidification of 3. BAC with acid addition and
BAC effluent to pH 6.5 with HCl and then UF. Then, the effluent was UF: 46% TOC removal

106
further treated using CDI process.
Municipal RO brine Lab-scale The brine was dosed with 4 mM H2O2 and then exposed to UV UV/H2O2 treatment followed by Not evaluated [108]
irradiation at the fluence rate of 13 mJ/cm2·s. Then, the brine was BAC resulted in 60% COD
passed through BAC column packed with GAC and with EBCT of removal.
60 min.
Municipal RO brine Lab-scale Municipal RO brine was ozonated at the dosage of 6 mg O3/L for Ozonation increased TOC The pre-treatment decreased CDI fouling by 50% [21]
20 min. The ozonated brine was fed to a BAC column packed with removal of BAC from 23 to 70%
GAC and with EBCT of 60 min. The BAC effluent was further treated
with CDI process.
Microbial fuel cell Not indicated Lab-scale The microbial fuel cell had four chambers, i.e., the anode chamber, 79% TDS removal Not evaluated [110]
the acid-production chamber, the desalination chamber, and the
cathode chamber. A bipolar membrane was between the anode and
acid production chambers, an anion exchange membrane was placed
between the acid production and desalination chambers, and a
cation exchange membrane was between the desalination and
cathode chambers.
Microalgae Not indicated Batch Chlorella sp. ZTY4 and Scenedesmus sp. LX1 were incubated under 60–80% Ca2+ removal; 56% Not evaluated [112]
experiments intermittent light (light:dark ratio is 14:10). The light intensity was Mg2+ removal
55–60 μmol/m2·s and temperature was 25 °C.
Dye wastewater RO Lab-scale Chlorella sp. was incubated under continuous light with intensity of Not reported Not evaluated [113]
brine 80 μmol/m2·s at 25 °C.
Desalination 441 (2018) 96–111
 G.U. Semblante et al.

Table 7
Performance and cost evaluation of potential pre-treatment methods. The estimated cost and removal efficiencies, e.g., very high (> 80%), high (61–80%), moderate (41–60%), low (20–40%), very low (1–20%), are
derived from literature focusing on treatment of RO brines unless specified otherwise.
Method Removal efficiency Capital cost Operating cost Other comments References

Hardness Silica Salinity Organic

compounds

Conventional precipitation Very high (Ca2+); Moderate to high removal None Very low 0.275 USD/m3 0.554 USD/m3 Removal depends on brine [32,48]
low to moderate if pH > 10 characteristics
(Mg2+)
a a
Seeded chemical precipitation Very high (Ca2+); Moderate to high if None Very low 10.8 USD/m3 (SPARRO) 0.06 USD/m3 (SPARRO) Removal depends on brine [17,44,46]
low to moderate pH > 10 characteristics
(Mg2+)
b
Chemical coagulation None Very low if pH ≤ 7 None Moderate to – 0.09 USD/m3; c0.12 USD/m3 Produces chemical sludge [54,55,57,58]
high
d 3 d 3
Electrocoagulation Moderate to very Moderate to high None Moderate to 0.08 USD/m 0.19 USD/m Produces less sludge compared to [70,72,75,80]
high high conventional coagulation/flocculation
in other treatment contexts.
e
Ion exchange High Low to high (Depending on None None – 0.08–0.21 USD/m3 Performance depends on type of ion [85,86]
the type of ion exchange exchange resin
resin)
f f
Nanofiltration Moderate to very Moderate Moderate Moderate to 0.03 USD/m3 0.09 USD/m3 Water recovery is limited by fouling [92,93,97]

107
high high
Adsorption (activated carbon) Low Moderate None None – – Organic adsorption can be improved [15,54]
with salinity
g g
Advanced oxidation processes None None None High 111 USD/m3 (ozonation); 7.9 USD/m3 (ozonation); High capital and operating cost [102,103,109]
g g
(ozonation and UV/H2O2) 187 USD/m3 (UV/H2O2) 5.3 USD/m3 (UV/H2O2)
Activated sludge None None None Low Not reported Not reported Can remove PO43− and SO42− [29,106]
g g
Biological activated carbon None None None Low to high 269 USD/m3 2.6 USD/m3 High organic removal achieved only [21,107–109]
when coupled with physico-chemical
treatment or AOPs
Microbial fuel cell Unknown Unknown High None – – Produces acid and base; however, ion [110]
transfer efficiency is very low
Microalgae cultivation Moderate to high Unknown Unknown None – – Produces valuable biomass; however, [112,113]
microalgae is susceptible to heavy
metals

a
Estimated cost of SPARRO for treatment of brackish mine service water as of 1988 [46].
b
Estimated operating cost of mining greywater treatment by PACl, alum, or FeCl3 at the dosage of 100–1200 mg/L; energy and sludge disposal costs are not included [57].
c
Estimated operating cost of metalworking fluid wastewater treatment by alum (500 mg/L); includes energy and sludge disposal costs [58].
d
Capital and operating cost for greywater treatment using Al electrodes, including electricity and sludge disposal [80].
e
The typical operating cost of wastewater treatment by ion exchange process.
f
Capital and operating cost of surface water treatment plant (18,000 m3/d) by NF operating at 83% water recovery with driving pressure of 7 bar [97].
g
Capital and operating cost of potable water production plant (37,854 m3/d). For ozonation, dosage is 8.65 mg/L [109].
Desalination 441 (2018) 96–111
G.U. Semblante et al. Desalination 441 (2018) 96–111

Less scaling and fouling

Priority research due to pre-treatment
Targets for removal Potenal pre-treatment opons areas for ZLD
Chemical Opmize to reduce operang cost; M
Membrane
Hardness Water
precipitaon Combine with other processes to process
remove silica and organics

Chemical Combine with other processes to

coagulaon remove hardness and silica

Brine
Less brine
Electro Elucidate removal mechanisms;
Brine volume
coagulaon Perform cost analysis

Silica Thermal Further

process treatment
Ion exchange for re-use
Use brine as regenerant; combine
with other processes to remove
organics

Nanofiltraon Develop strategies to prevent

organic fouling Solid waste

Organics

Adsorpon Explore low cost adsorbents;

combine with other processes to
remove hardness and silica

Fig. 2. Potential brine pre-treatment options for hardness, silica and organic removal, and the priority research areas towards achieving ZLD.

3.8.4. Microalgae
Microalgae are photosynthetic microorganisms that subsist on sun-
light, nutrients and carbon source [111]. Due to their high seed oil
content, microalgae can be converted to biodiesel and animal feed [111].
Cultivating microalgae is a potential approach to recycle resources from
brine and to produce biomass with economic value [112,113]. Wang
et al. [112] cultivated two microalgal strains, Chlorella sp. ZTY4 and
Scenedesmus sp. LX1, on RO brines (TDS = 3400–3600 mg/L;
Mg2+ = 70–120 mg/L; Ca2+ = 280–390 mg/L). Approximately 60–80%
of Ca2+ and 56% of Mg2+ were removed. The removal mechanism was
precipitation of CaCO3 due to increase in pH in the culture medium
caused by microalgal growth. The biomass production rate and lipid
content were relatively high (i.e., 318 mg/L and 31%, respectively),
which means that microalgae could thrive on RO brines. However, some
heavy metals have negative impact on microalgae. For instance, Cu2+
concentration of > 0.032 mg/kg is toxic to Chlorella sp. [113]. To work
around this issue, Zhang et al. [113] first added EDTA to dye industry RO
brine (Cu2+ = 12.8 mg/kg) to remove Cu2+ by chelation. This allowed
Chlorella sp. to grow on brine with a moderate biomass production of
106 mg/L. These studies indicate that microalgal cultivation might be
applied for treatment of brines as long as the heavy metal concentrations
are below the microalgal growth inhibitory levels.
3.8.5. Evaluation of biological approaches
Many of the studies evaluated the performance of biological pro-
cesses using municipal RO brines that have relatively low hardness and
salinity (Table 6). Only a few studies applied biological processes in
industrial brines [106,113]. The main concern of industrial brines is the
detrimental effect of high inorganic concentrations on microorganisms.
For example, it has been observed that feed with NaCl concentration
of > 10,000 mg/L caused significant cell destruction and a decrease in
COD removal efficiency in activated sludge [114]. It has also been
found that high heavy metal concentrations are toxic to microalgae
(Section 3.8.4). Nonetheless, some microorganisms can adapt to
stressful environments. Wang et al. [115] observed that denitrifiers
(e.g., Nitrosomonas marina) thrived in a lab-scale membrane bioreactor
(MBR) with highly saline feed (NaCl = 40,000 mg/L). Pradhan et al.
[116] also observed that microorganisms in a lab-scale BAC acclima-
tized to highly saline municipal RO brine (TDS = 16,000 mg/L). Con-
sequently, the combined UV/H2O2 and BAC process was able to achieve
60 and 90% of DOC and ammonia removal, respectively. These findings
suggest that certain microbial groups can survive on brine. It is
worthwhile to identify these microorganisms and to further evaluate
the feasibility of using them as means for hardness and/or organic re-
moval.
4. Comparison and future prospects
Table 7 summarizes the performance and cost of the existing and
potential pre-treatment technologies for ZLD. The common pre-treat-
ment process, chemical precipitation, can be used to remove hardness
and consequently, mitigates downstream membrane scaling from cal-
cium precipitates. However, it is unable to sufficiently address silica
scaling and organic fouling. Seeded chemical precipitation could en-
hance the precipitation of certain salts (e.g., CaHPO4), but overall it
offers little advantage over conventional chemical precipitation in
terms of silica and organic removal. Furthermore, hardness removal by
chemical precipitation process is hindered by temporal variation in
brine characteristics and presence of antiscalants (Section 3.1.3). The
process is further encumbered by high cost of chemicals (Table 7).
Despite these disadvantages, chemical precipitation remains indis-
pensable in membrane-based ZLD given that other pre-treatment

108
G.U. Semblante et al.
technologies are yet to be tested in pilot- or full-scale plants to provide
their technical and economic feasibility.
Several technologies have demonstrated high capacity for organic
removal including chemical coagulation, EC, NF, adsorption and BAC
processes (Table 7). Meanwhile, EC and ion exchange processes show
potential for silica removal (Table 7). A framework for brine manage-
ment in ZLD can be developed depending on brine characteristics and
the availability of pre-treatment processes (Fig. 2). Future research
should focus on combining different processes to manage brines with
considerable levels of scale precursors and organics. Further in-
vestigation using pilot-scale systems is needed to determine operating
cost, which is one of the major factors that determine the practical
application of these technologies in ZLD. For example, the coagulation
processes have relatively low capital cost, but their operating cost
might be high due to chemical consumption and sludge management
(Table 7). The adsorption processes have finite adsorption capacity, so
the majority of the operating cost is due to regeneration chemicals and
cleaning processes. NF offers relatively consistent performance and
does not produce sludge, but it has high capital cost, and its efficiency
could be limited by organic fouling. A careful consideration of brine
properties, removal requirements and costs must be performed in order
to design a suitable process combination (Fig. 2).
It is noted that some technologies are not suitable as pre-treatment
processes for industrial brines. These include AOPs, activated sludge,
microbial fuel cell and microalgae. AOPs have very high treatment costs
(Table 7). Moreover, the oxidation efficiency of AOPs decreases when
applied in complex solutions such as brine due to competition amongst
inorganic and organic constituents (Section 3.7). Activated sludge has
limited treatment capacity (nitrogen and sulfate removal only) and
requires additional carbon source to function (Section 3.8.1). Microbial
fuel cell technology is mostly in the development stage; extensive re-
search is required to address key issues (e.g., low ion transfer efficiency)
before scaling up is even considered (Section 3.8.3). Finally, microalgae
is susceptible to heavy metals that are usually present in industrial
brines (Section 3.8.4).
5. Conclusion
Brine pre-treatment is key to the realization of membrane-based
ZLD. Chemical precipitation, the most widely used pre-treatment in the
industry, is encumbered by the temporal variation in brine character-
istics, occurrence of antiscalants and high operating cost. Ion exchange,
EC and NF processes show great potential to remove inorganic scale
precursors. In addition, chemical coagulation, EC, nanofiltration and
adsorption (i.e., PAC, GAC, and BAC) processes have demonstrated
remarkable capacity to remove organic foulants. It would be useful to
determine the technical and economic feasibility of applying combi-
nations of these technologies to manage problematic brines, e.g., those
from industrial sources with high hardness, silica and organic content.
Biological processes such as activated sludge, microbial fuel cell and
microalgae show little potential as pre-treatment due to narrow scope
of treatment, low performance and toxicity of brine to microorganisms.
Acknowledgements
The work is supported by the National Research Foundation
Singapore, Sembcorp Industries Ltd. and National University of
Singapore under the Sembcorp-NUS Corporate Laboratory.
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