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Integrated green membrane distillation-microalgae bioremediation for

arsenic removal from Pengorak River Kuantan, Malaysia

Siti Khadijah Hubadillah, Mohd Hafiz Dzarfan Othman, Paran Gani,

Norshuhaila Mohamed Sunar, Zhong Sheng Tai, Khong Nee Koo,
Mohamad Arif Budiman Pauzan, Nurul Jannah Ismail

PII: S0255-2701(20)30453-0
DOI: https://doi.org/10.1016/j.cep.2020.107996
Reference: CEP 107996

To appear in: Chemical Engineering and Processing - Process Intensification

Received Date: 1 March 2020

Revised Date: 8 May 2020
Accepted Date: 7 June 2020

Please cite this article as: Hubadillah SK, Othman MHD, Gani P, Sunar NM, Tai ZS, Koo KN,
Pauzan MAB, Ismail NJ, Integrated green membrane distillation-microalgae bioremediation
for arsenic removal from Pengorak River Kuantan, Malaysia, Chemical Engineering and
Processing - Process Intensification (2020), doi: https://doi.org/10.1016/j.cep.2020.107996

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Integrated green membrane distillation-microalgae bioremediation for arsenic removal
from Pengorak River Kuantan, Malaysia
Siti Khadijah Hubadillaha, Mohd Hafiz Dzarfan Othmana*, Paran Ganib,
Norshuhaila Mohamed Sunarc, Zhong Sheng Taia, Khong Nee Kooa, Mohamad Arif Budiman
Pauzana, Nurul Jannah Ismaila

a
Advanced Membrane Technology Research Centre (AMTEC), School of Chemical and
Energy Engineering (SCEE), Faculty of Engineering, Universiti Teknologi Malaysia, 81310
UTM, Skudai, Johor, Malaysia.
b
School of Biological Sciences, Faculty of Science and Technology, Quest International
University Perak, No 227, Plaza The Teng Seng, Jalan Raja Permaisuri Bainun, 30250 Ipoh,

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Perak, Malaysia.
c
Department of Civil Engineering Technology, Faculty of Engineering Technology,

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Universiti Tun Hussein Onn Malaysia, 86400, Parit Raja, Batu Pahat, Johor, Malaysia

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*Corresponding email: hafiz@petroleum.utm.my
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Graphical Abstract
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Highlight

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 A novel integrated system of membrane distillation and microalgae bioremediation
for green removal of arsenic.

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 Botryococcus sp. used as microalgae bioremediation in integrated system.


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System demonstrates an excellent arsenic rejection of 100% and a stable flux of
23.3 kg/m2h.
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 A development of wastewater treatment technologies with zero waste discharge.
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Abstract
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This study introduces an integrated system of direct contact membrane distillation

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(DCMD) and microalgae bioremediation for green removal of arsenic from the polluted river

water. An inexpensive hydrophobic kaolin hollow fiber membrane (h-KHFM) was fabricated

and used in the DCMD process for arsenic treatment on the polluted river water. The membrane

demonstrates an excellent arsenic rejection of 100% and a stable flux of 23.3 kg/m 2h

throughout the prolonged operation of 70 hours. The performance of this membrane was

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compared with those of NF and RO; the results indicate superior performance of h-KHFM over

the latter two processes in terms of permeate flux, arsenic rejection, as well as the performance

flexibility and consistency at various pH conditions. The arsenic-rich retentate of the DCMD

process is then bioremediated using Botryococcus sp. with an initial cell concentration of 1 x

106 cells/mL at the outdoor conditions. The findings show that Botryococcus sp. successfully

grow in the retentate with a common microalgae growth pattern during the 20 days test period,

which indicates the potential and feasibility of this integrated system for the arsenic retentate

management. This study is pioneer and could provide an insight for the development of

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wastewater treatment technologies with zero waste discharge.

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Keywords: Membrane Distillation; Ceramic Membrane; Kaolin; Arsenic; Microalgae;

Bioremediation
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1 Introduction
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Generally, drinking water is produced from groundwater, surface water, rainwater, or

recycled water. Groundwater is the water found underground in aquifers, whereas surface water

is found in rivers, lakes and seas. Groundwater is regarded as the major source of drinking
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water in many regions, especially in the developing countries such as Bangladesh, Cambodia,

India, Pakistan, China, Taiwan, Thailand and Nepal [1]. The arsenic contamination of the
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groundwater has been one of the main concerns in these countries. The arsenic contamination
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of the drinking water sources would lead to a widespread of health effects such as weakness,

chronic respiratory diseases, peripheral neuropathy, liver fibrosis and poor growth, and it is

lethal if there is excessive intake [2, 3]. Recently, there have also been reports on the arsenic

contamination of surface water. For example, in 2011, the surface water in the village of

Pesariis in the Carnic Alps (North East of Italy) was found contaminated with high levels of

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arsenic of more than 900 ppb [4]. In addition, thousands of fish were found dead near the

Pengorak River and Beach, Pahang, Malaysia in 2015. The specimen results showed an

extremely high concentration of arsenic (101,500 ppb) in the fish bodies [5]. The arsenic

contamination was caused by nearby bauxite mining and this issue remains unsolved until

today [6]. In Malaysia, 97% of the drinking water is obtained from surface water, which is used

for agricultural, domestic and industrial needs [7]. Besides, there are many countries obtain the

drinking water from surface water too, such as Brazil, Russia and Canada. Hence, the treatment

of arsenic contaminated water is essential to reduce the environmental and health impacts.

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Various technologies have been introduced for the removal of arsenic from water

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sources, including precipitation, coagulation, electrocoagulation, reverse osmosis,

electrodialysis, adsorption, ion exchange, and membrane filtration. Conventionally,

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coagulation and flocculation are among the most commonly used methods for arsenic removal.

In 1996, Hering et al conducted bench-scale studies in model freshwater systems to investigate

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various parameters on arsenic removal during coagulation with ferric chloride [8]. However, it
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was found that As (V) has better removal than As (III) in the process. At the same time, it was

observed that As (V) removal was significantly decreased whereas at high pH, As (V) removal

was increased with presence of calcium content. Bellack pioneering ion exchange technique
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for arsenic removal by demonstrating activated alumina and bone char as the synthetic resin

[9]. It was proved that this technique is economical. A year later, Lee and Rosehart investigated
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the removal of arsenic from wastewater using ion exchange resin and activated carbon was
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used as sorption media [10]. However, the removal of arsenic was highly dependent on the pH

of the solution.

Recently, membrane distillation (MD) has received increasing attention in water

purification applications including desalination and heavy metals removal. The removal of

arsenic via MD was first reported in 2008 with excellent As(III) and As(V) rejections of 100%

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[11]. MD is a combination of thermal and membrane processes in which heat is applied to

vaporize the feed solution, followed by the transport of vapor through the membrane pores. In

addition, MD process is not dependent on pH solution. Hydrophobic membrane is applied in

this process which allows the passage of vapor (water) and refrains the transport of liquid

solution with unwanted solutes through the pores to the permeate side of the membrane. The

transport of vapor is driven by the pressure difference between two sides of the membrane

pores [12]. MD operates at relatively much lower pressure compared to some other pressure

driven membrane separation processes such as reverse osmosis (RO). RO membranes have the

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smallest pore size (around 0.1 nm) and best removal rate. For example, Akin et al. compared

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two types of RO membranes (SWHR and BW-30) on As(III) and As(V) removal under

different operating pressure ranging from 10 to 35 bar [13]. Schmidt et al. set up a pilot study
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on arsenic removal from groundwater located in India using a small-scale RO system [14]. A

99% of rejection was obtained and the value was in compliance with the WHO Guideline value
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and the National India Standard of 10 µg/L. In addition, a discharge well also has been
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proposed in the work to be an option for safe disposal of the RO concentrate. Since the

separation mechanism of MD is based on the vapor-liquid equilibrium, it does not have high

requirements on the membrane pore size. In fact, the MD membrane exhibits relatively larger
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pore size than those of the pressure driven membrane separations.

Today, ceramic membranes are known as the “innovative technology” for MD

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applications [15-17]. Ceramic membranes exhibit several superior advantages over their
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polymeric counterparts, such as the ability to withstand harsh conditions (e.g., high

temperature, extreme pH conditions, etc.). Unfortunately, ceramic membranes are mainly

fabricated from alumina, which requires a high sintering temperature of up to 1500˚C to reach

a compromise between the mechanical strength and porosity [18]. This also results in lengthier

fabrication process due to longer sintering process when extremely high temperature is

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involved. In addition, alumina is also known as a high cost material, thus making the ceramic

membranes extremely expensive. Hence, the development of low-cost ceramic membranes is

of the utmost importance. In our previous works, low-cost hydrophobic ceramic membranes

derived from natural ceramic sources (kaolin clay and agricultural rice husk waste) were

successfully introduced for MD applications [6, 19]. These membranes could be the

outstanding candidates for the treatment of arsenic wastewater. Kaolin hollow fiber membranes

(h-KHFM) demonstrated excellent 100% arsenic rejection with high permeate flux using direct

contact MD (DCMD) [6]. However, the long-term performance of h-KHFM had yet to be

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determined. In this study, we attempted to investigate the performance of h-KHFM for a

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prolonged period of 70 hours. Subsequently, the performance of h-KHFM in DCMD was

compared with nanofiltration (NF) and reverse osmosis (RO) membranes in terms of permeate

flux and arsenic rejection.

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Waste disposal management has been the major challenge for every wastewater treatment
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plants. In DCMD arsenic wastewater treatment, the retentate contains very high concentration
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of arsenic, hence should be properly managed. Since the first introduction of MD in 1963, no

study has been reported on the waste disposal management for MD applications. Hence, in this

work, we introduce the microalgae bioremediation for the waste disposal management on the
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concentrated arsenic retentate of the DCMD process. After the DCMD process, the retentate

was channeled into microalgae pond containing Botryococcus sp. for bioremediation. Today,
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microalgae bioremediation has gained increasing attention due to several advantages such as
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solar energy-driven, ecofriendly, as well as simultaneous carbon mitigation and production of

valuable side products [20, 21]. The use of microalgae for the removal of heavy metals and

water treatment has been well reported over the past 40 years [22, 23]. The microalgae remove

the toxic heavy metals from the aqueous effluents through metabolic activity and passive

uptake [23]. In 1988, Yamaoka et al. was the first to report the arsenic removal through

6
phycoremediation [24]. They used microalgae Dunaliella sp. in which they obtained from

Hiroshima Fisheries Experimental Station, Japan. In the study, they harvested the microalgae

in 5 dm3 cultures at 23 °C and were constantly bubbled with air. Thereby, light was used with

40W power grove cool white lamps at intensity of 6000 lux at the surface of water. The

integration of MD with microalgae bioremediation in this study is believed to overcome the

issues related to treatment waste disposal, as well as to provide an insight for the development

of wastewater treatment technologies with zero waste discharge.

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2 Methodology

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2.1 Hydrophobic kaolin ceramic hollow fiber membrane (h-KHFM)

h-KHFM with thickness 240 µm were fabricated via phase inversion/sintering technique.
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First, a suspension with kaolin loading of 37.5 wt% was prepared. Next, the suspension was

extruded through a tube-in-orifice spinneret to form hollow fiber precursors followed by phase
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inversion process. Then, the precursors were subjected to sintering process at 1300˚C, and
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hollow fiber membranes were obtained. The hydrophilic h-KHFMs were converted into

hydrophobic via surface modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. More

details on the fabrication of hydrophobic h-KHFM could be found in our previous work [6].
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The h-KHFM exhibited an asymmetric structure consisting of finger and sponge-likes pores

with a water contact angle of 145.7˚ [6].

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2.2 Characterization of arsenic-contaminated river water sample

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The water sample was collected from Pengorak River, Kuantan, Malaysia (3˚58’0.1”N,

103˚24’16.9”E). The water sample was transferred into an acid washed sample bottle and

immediately preserved in a refrigerator at a temperature below 4˚C. Prior to the

characterization, the sample was filtered through a Whatman membrane filter with a pore size

of 0.45 mm to remove the microorganisms and fine suspended solids. The sample was then

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characterized by the following analyses: Atomic Absorption Spectroscopy (AAS, Aanalyst

800), turbidity meter (Turbidity: 2100Q, Hach Turbidemeter, USA), total dissolved solid (TDS

portable meter, EC300, YSI. Inc), chemical oxygen demand (COD, DR 5000, Hach

Spectrophotometer, USA), meanwhile, total phosphorus (TP), total nitrogen (TN) and total

organic carbon (TOC) were analysed using a DR 6000 Spectrophotometer (Hach, USA)

according to Method10127, Method 10072, and Method 10129, respectively. Table 1

demonstrates the characterization results of the river water sample. The results indicated that

the water sample was heavily contaminated by arsenic (107,500 ppb).

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Table 1: Characteristics of the river water sample collected from Pengorak River, Kuantan,
Malaysia

2.3 DCMD integrated with microalgae bioremediation

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The arsenic-contaminated river water sample was treated using a laboratory scale DCMD

setup equipped with a h-KHFM module. After removing the suspended solids using a Whatman
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membrane filter, the river water sample was placed in a feed reservoir. The conditions of the

DCMD process were set as follows: feed temperature: 60˚C; permeate temperature: 10˚C; feed
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flow rate (Qf): 42 kg/hr; and permeate flow rate (Qp): 30 kg/hr. The concentration of arsenic in

the feed and permeate were determined via graphite furnace absorption spectroscopy using a
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Perkin Elmer SIMAA 6000 system equipped with a Zeeman-effect background correction

system, an electrothermal atomizer with transversely heated graphite tube and an AS-72
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autosampler. An arsenic electrodeless discharge lamp (Perkin Elmer) was used as the radiation

source. The current of the lamp was set at 380 mA, and a primary resonance line of 193.7 nm

was used for all the measurements with a spectral bandwidth of 0.7 nm. The analytical

measurements were based on the peak area. The volumes of the tested samples (feed and

permeate) and chemical modifiers injected into the furnace were fixed as 20 and 5 μL,

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respectively. Argon gas with a purity of 99.996% was purged and the gas flow was stopped

during atomization [25]. The permeate flux, Jv (kg/m2 h1) of h-KHFM was measured using

Equation (1).

∆𝑊
𝐽𝑣 = (1)
𝐴∆𝑡

where ∆W is the weight of the permeate collected (kg) over a pre-determined time, ∆t of the

DCMD process (hour), and A is the effective membrane area (m2). The arsenic rejection

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efficiency, R (%) was calculated according to Equation (2).

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𝐶𝑓 − 𝐶𝑝
𝑅= 𝑥 100% (2)
𝐶𝑓 -p
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where Cf and Cp are the concentrations of feed and permeate, respectively. After the DCMD

process, the retentate was channeled to the retentate tank for bioremediation using
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Botryococcus sp. The overall setup of the integrated DCMD and microalgae bioremediation

system is as depicted in Figure 1.

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Figure 1. Overall setup for the integrated DCMD and microalgae bioremediation system
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2.4 Culture of microalgae Botryococcus sp.

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The freshwater microalgae Botryococcus sp. was acquired from a tropical rainforest

located in the southern region of Peninsular Malaysia (between 2˚30.711”N, 103˚20.984”E and

2˚30.740”N, 103˚20.99”E) [26]. The microalgae were cultured outdoors at the temperature of

28 to 38˚C under light with the intensity ranging from 2.7 to 243 μ mol/m2s for 14 days. The

cell concentration was counted using a Neubauer haemocytometer, and a cell concentration of

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1 x 106 cells/mL was used for the microalgae bioremediation process of the DCMD retentate.

The main grid of the Neubauer haemocytometer contains nine squares with the dimension of 1

mm x 1 mm. The depth of each square is 0.1 mm and the volume of each square is 0.0001 mL.

The cell concentration, C (cells/mL) can be calculated using Equation 3.

𝑇𝑐
𝐶= 𝑥 104 (3)
𝑛

where Tc is the total number of cells counted and n is the number of squares. The microalgae

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bioremediation of the DCMD retentate was carried out for a period of 20 days.

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3 Results and discussion

3.1 Performance of h-KHFM in DCMD

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Figure 2(A) shows the permeate flux and arsenic rejection of the h-KHFM membrane
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during the 70-hours DCMD test period. The permeate flux is 22.3 kg/m2h at the beginning of
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the test and slightly fluctuates for about 20 hours. The flux then remains stable for the next 50

hours. The fluctuation at the early stage of the test is probably due to the instability of silica
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under hydrothermal conditions. It has been known that the silica-based membranes are prone

to structural degradation when exposed to water [27, 28]. This is attributed to the physisorption
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of water molecules on the silanol (Si–OH) groups, followed by the hydrolysis reaction with the

nearby siloxane (Si–O–Si) bonds. These mobile Si–O–Si groups migrate across the membrane
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pores and undergo consequent condensation reactions with other Si–OH groups, resulting in

the change of membrane pore structures [29]. As can be seen, the flux fluctuation at the first

20 hours of the test is not significant, indicating the change of the pore structure is somewhat

impeded. This could be attributed to two reasons: (a) the hydrophobic outer surface of h-

KHFM, and (b) the presence of metal oxide impurities in kaolin. First, the removal of the

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hydroxyl groups on the outer surface of h-KHFM through the reactions with FAS molecules

reduces the tendency of pore structural degradation during MD process. However, as illustrated

in Figure 2(B), the inner structure of h-KHFM is unmodified and remains hydrophilic. This

would lead to the rehydration of the silica structure when the membrane is in contact with the

cold permeate, as indicated from the initial unstable flux performance. Second, kaolin is made

up of various metal oxides as reported in our previous study [30]. The presence of other metal

oxides hinders the mobility of the Si–O–Si groups, and consequently reduces the tendency of

pore structural degradation [27]. After 20 hours, the structural changes of the membrane pores

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begin to equilibrate as indicated from the stable flux performance [28].

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Figure 2. (A) Permeate flux and arsenic rejection of the h-KHFM during the 70-hours DCMD
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test period; and (B) Schematic diagram of h-KHFM structures
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Moreover, the stable flux of ~23.3 kg/m2h and excellent arsenic rejection of 100% also
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indicates that h-KHFM does not experience any fouling throughout the MD test period. The

high hydrophobicity of h-KHFM surface bestows the membrane with enhanced anti-fouling

properties and resistance towards pore wetting [31]. Interestingly, the hydrophilic membrane
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with hydrophobic top surface structure (Figure 2(B)) also contributes to the high flux

performance of h-KHFM. During the MD process, the thick hydrophilic membrane layer is
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filled with cold water permeate, which leads to shorter vapor transport distance and
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consequently lowers the vapor transport resistance [32]. The flux performance of h-KHFM is

relatively higher than that achieved by polypropylene (PP) membrane in a study by Husnain et

al. [33]. In their study, an arsenic rejection of more than 99.9% with the flux of ~15 kg/m2h

was obtained via the integration of forward osmosis and DCMD. It is interesting to be noted

here that conductivity and turbidity is reduced to 0.5 µs/cm and 1 NTU meanwhile no detection

11
can be obtained for TDS and COD. This result proved that MD able to produce pure water

from contaminated water by allowing only vapor through the h-KHFM. Figure 2(C) shows a

schematic diagram on materials balance of membrane separation in this study. From the figure,

the product recovery, r and global rejection, R can be calculated as follow:

Product recovery, r = (QP/QF) x 100%

= (30/42) x 100%

= 71.4%

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Global rejection, R = (1 – CP/CF) x 100%

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= (1 – 0/107500) x 100%

= 100% arsenic rejection

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Figure 3 demonstrates the SEM and AFM images, as well as the contact angles of h-

KHFM before and after 70 hours MD process. It can be observed that there is no significant
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change in the membrane surface structure after the MD test. This has further proven that no

fouling has occurred throughout the process. The contact angle of h-KHFM remains stable at
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about 146˚ after the prolonged process. The consistent membrane contact angle indicates that

the hydrophobic FAS layer is strong and stable at the MD operating conditions without
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experiencing any deterioration during the long operation duration [34]. In addition, the

membrane demonstrates a high surface roughness (Ra) of 0.407 μm before the test. The surface
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roughness slightly decreases to 0.389 μm after prolonged process. The rough membrane surface

minimizes the contact area between the liquid and membrane surface, hence, contributes to the

non-wettability and anti-fouling properties of the hydrophobic h-KHFM surface [35].

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Figure 3. SEM and AFM images, as well as the contact angles of the h-KHFM before and after

the DCMD process

3.2 Potential evaluation of MD with other processes in arsenic removal

MD is relatively new for arsenic removal applications. In this study, a comparative

evaluation was done on MD with other pressure driven membrane separation technologies

reported in literature such as NF and RO, to identify the potential of MD for arsenic removal

applications [36]. Figure 4(A and B) illustrates the separation performances of MD, NF and

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RO membranes in terms of permeate flux and arsenic rejection. Noticeably, the NF membrane

demonstrates the highest permeate flux (37.4 kg/m2h) whereas it is the lowest for RO with the

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value of 10.5 kg/m2h. As can be seen from Table 2, a high pressure of 10 bar was applied for
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both NF and RO separations which are energy consuming. As a result, the NF membrane shows

higher flux performance than MD with the aid of pressure driven process despite having
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smaller pore size than that of MD (Table 2). On the other hand, MD does not involve high
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pressure operation; in fact, a low pressure of less than 1 bar was applied in this study.

Accordingly, Koeman-Stein et al. reported that the typical energy cost for RO process was 3

kWh/m3 whereas it was 0.75 kWh/m3 for MD [37]. In addition, MD/h-KHFM is capable to
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achieve 100% arsenic rejection efficiency which is comparable to RO process. On the contrary,

NF exhibits low arsenic rejection of less than 30%. In short, the comparative results show that
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MD/h-KHFM can be a promising technology for arsenic treatment applications due to its high
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flux and arsenic removal efficiency at low operating pressure conditions. The effect of pH on

the arsenic rejection of MD/h-KHFM, NF and RO were also compared as depicted in

Figure 4(C). It is found that both NF and RO processes show decreasing arsenic rejection at

lower pH. The arsenic rejection performance of NF and RO membranes are relied on two main

factors, namely 1) membrane pore size, and 2) electrostatic exclusion. According to Qu et al.

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[38], NF and RO are negatively charged hydrophilic pressure-driven membrane processes in

which the electrostatic exclusion plays an important role. At the acidic and neutral pH (pH 3 to

7), arsenic exists as neutral solute, whereas it is monovalent anion at pH 10. As observed, the

arsenic rejection is higher when the pH > 7 as H3AsO3 is converted into H2AsO3-. More detailed

discussion on the arsenic removal mechanisms of NF and RO can be found elsewhere [39]. On

the other hand, the arsenic rejection performance of MD/h-KHFM is consistent at 100%

without being influenced by pH. This indicates the superior flexibility and consistency of MD

process over other pressure-driven membrane processes for the arsenic wastewater treatment

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applications at various pH conditions.

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Figure 4. Comparison between MD/h-KHFM and other pressure-driven membrane processes
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in literature in terms of (A) permeate flux, and (B) arsenic rejection [36], and (C) different pH
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conditions [36]

Table 2 Comparison between the properties of membranes used for NF and RO, as well as
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MD/h-KHFM

3.3 Microalgae bioremediation using Botryococcus sp.

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As can be seen from images in Figure 5(A), the DCMD retentate appears brown on day

1 and turns green on day 20, indicating the growth of Botryococcus sp.in the concentrated
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arsenic contaminated water (112,000 ppb). Figure 5(B) displays the trend of the microalgae

growth throughout the 20 days test period. The result shows that the Botryococcus sp.
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experiences a typical microalgae growth [40, 41]. The initial microalgae concentration is

100,000 cells/mL and no significant growth is observed on the first 3 days. A gradual increase

in the cell concentration occurs between day 4 to 13 with an optimum cell concentration of

480,000 cells/mL, signifying the occurrence of the second growth phase (exponential phase).

On day 13, the microalgae experience a decline in relative growth with the cell concentration

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drops to 440,000 cells/mL. At this phase, the cell division starts to slow down due to the lack

of nutrients, light and carbon dioxide, as well as the changes of some other physical and

chemical factors that limit the microalgae growth [41]. The microalgae growth remains stable

from day 15 to 20 with a value of 412,000 cells/mL. During this stationary phase, the limiting

factor and growth rate are balanced, resulting in a relatively constant cell density. In this study,

Botryococcus sp. does not experience the final death phase probably due to insufficient culture

age. Similar microalgae growth trend has also been reported in literature on the arsenic

contaminated wastewater treatment, such as Ostreococcus tauri [42], Chlorella pyrenoidosa

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[43] and Phaeodactylum tricornutum [44].

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In this study, mixotrophic culture conditions was provided for the microalgae growth.

Previous studies have shown that some microalgae exhibit higher growth rates, biomass yields
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and even lipid contents under mixotrophic conditions compared to those of photoautotrophic

conditions. Bhatnagar et al. [45] reported the mixotrophic cultivation of C. minutissima

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resulted in a biomass production of 4.44 times higher that obtained via photoautotrophic
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cultivation. Liang et al. [46] found that the mixotrophic growth of C. vulgaris (UTEX 259)

resulted in a high biomass concentration of 1.70 g/L. The high cell growth in this study shows

that Botryococcus sp. can successfully be grown in the wastewater containing high arsenic
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concentration which consequently can help to solve the problem related to the waste disposal

management of DCMD process. In addition, macronutrient such as phosphorus and nitrogen

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and arsenic as micronutrient in Pengorak River play a vital role in regulating the metabolism
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and finally the growth of microalgae. Accordingly, Figure 5(C) show the decreasing trend for

arsenic in the feed containing Botryococcus sp during bioremediation process collected every

day. Interestingly, the arsenic concentration at 20 days is 8 ppb, in which the water is safe to

be discarded into Pengorak River or recycle. According to Oswald [47], microalgae

transformed heavy metals into non-hazardous materials so that the treated water can be safely

15
discarded or reused, whereas the microalgae can be converted into valuable products such as

bio-plasticizers. Herein, microalgae Botryococcus sp transform arsenic into methylated arsenic

species and arsenosugars species.

Figure 5 (A) Images indicating the Botryococcus sp growth in DCMD retentate containing

high concentration of arsenic; (B) the trend of Botryococcus sp growth throughout the 20 days

test period; and (C) the trend of arsenic reduction during bioremediation process

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4 Conclusion

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In this work, the h-KHFM demonstrates a consistent long-term performance for the

treatment of arsenic contaminated river water using the DCMD process. The membrane
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exhibits a steady flux of ~23.3 kg/m2h and an excellent arsenic rejection of 100% throughout

the 70 hours treatment period. In addition, the membrane does not experience any membrane
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fouling throughout process due to its highly hydrophobic surface that enhances the anti-fouling
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properties and resistance towards pore wetting. Interestingly, the development of the

hydrophilic membrane with hydrophobic top surface structure also contributes to the high flux

performance of h-KHFM. Moreover, the membrane also shows superior performance for
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arsenic wastewater treatment compared to those of the NF and RO processes in terms of

permeate flux, arsenic rejection as well as the performance flexibility and consistency at
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various pH conditions. Lastly, the concentrated arsenic retentate of the DCMD process are
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bioremediated in which the Botryococcus sp. successfully grows in the retentate during the 20

days test period. The findings of this study indicate the potential and feasibility of the

integration of DCMD with microalgae bioremediation process for the arsenic retentate

management, which consequently could help to solve the problems related to retentate disposal

and provide insights for the development of treatment technologies with zero waste discharge.

16
Author statement

Authors Roles

Siti Khadijah Hubadillah First author of the manuscript. She is the main author
that responsible in both experimental and writing.

Mohd Hafiz Dzarfan Othman Dr. Hafiz is corresponding author for the work.
Experimental work done in this paper is under his supervision. All testing has been paid
using Dr. Hafiz’s grant. Prior of the submission, the manuscript has been checked by him.

Paran Gani Dr. Paran is responsible in microalgae growth. He

conducted the bioremediation process together with Dr. Siti Khadijah.

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Norshuhaila Mohamed Sunar Dr. Shuhaila is the researcher who was found the
microalgae Botryococcus sp. In this work, we used her microalgae with the best

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concentration obtained by her previous work.

Zhong Sheng Tai -p

Mr. Tai responsible in membrane distillation system set-
up. He also proofread the manuscript so that no grammar mistakes.
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Khong Nee Koo Miss Koo is responsible in water analysis testing.

Mohamad Arif Budiman Pauzan Mr. Budiman role is conducting a contact angle test.
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Nurul Jannah Ismail Miss Nurul Jannah helps in preparing the module for
membrane distillation system. She potted seven membrane in a module.
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Declaration of interest statement

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This manuscript is not published or in process to any other journal submission. The idea and
findings in the manuscript is original by the authors listed in the manuscript.

17
Acknowledgements

The authors gratefully acknowledge the financial supports from the Ministry of Higher

Education Malaysia under the Higher Institution Centre of Excellence Scheme (Project

Number: R.J090301.7809.4J430), Malaysia Research University Network (MRUN) Grant

(Project Number: R.J130000.7809.4L867) and Fundamental Research Grant Scheme (Project

Number: R.J130000.7809.5F161), Ministry of Science, Technology and Innovation (MOSTI),

Malaysia under International Collaboration Fund (ICF) and Universiti Teknologi Malaysia

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under the UTM Transdiciplinary Research Grant (Project number: Q.J130000.3509.05G75)

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and Collaborative Research Grant (CRG) (Project number: Q.J130000.2409.08G29). Ministry

of Science, Technology and Innovation (MOSTI), Malaysia under .

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Figures

Figure 1 Overall setup for the integrated DCMD and microalgae bioremediation

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system

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Figure 2 (A) Permeate flux and arsenic rejection of the h-KHFM during the 70-hours
DCMD test period; and (B) Schematic diagram of h-KHFM structures

Figure 3
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SEM and AFM images, as well as the contact angles of the h-KHFM before
and after the DCMD process
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Figure 4 Comparison between MD/h-KHFM and other pressure-driven membrane
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processes in literature in terms of (A) permeate flux, and (B) arsenic

rejection [27], and (C) different pH conditions [27]
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Figure 5 (A) Images indicating the Botryococcus sp growth in DCMD retentate

containing high concentration of arsenic; and (B) the trend of Botryococcus
sp growth throughout the 20 days test period
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Figure 1

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Figure 2

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Figure 3
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 Figure 4

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Figure 5

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Tables

Table 1 Characteristics of the river water sample collected from Pengorak River,
Kuantan, Malaysia

Table 2 (A) Permeate flux and arsenic rejection of the h-KHFM during the 70-hours
DCMD test period; and (B) Schematic diagram of h-KHFM structures

Table 1

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DCMD parameters Value
Arsenic (ppb) 107,500

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Conductivity (µs/cm) 47
Turbidity (NTU) 13
TDS (ppm)
COD (mg/L)
-p 51
6.8
Total phosphorus, TP (mg/L) 9.7
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Total nitrogen, TN (mg/L) 0.8
Total organic carbon, TOC (mg/L) 4.38
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Table 2
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Membrane NF RO MD/h-KHFM
process
Reference [27] [27] This sudy
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Membrane Polyamide Polyamide h-KHFM

Pore size 0.001 < 0.001 0.12
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Transmembrane 10 10 < 0.1

pressure (bar)

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