Intro

Textile industry sector is expanding day by day with the increasing demand of products.
Textile industry is one of the vast and imperative and it utilize textile auxiliaries, dyes and
chemicals in its processes. Textile industries generate bulk of wastewater due to use of dyes,
chemicals and other additives in its manufacturing processing. These processes require
abundant quantity of water leading to generation of wastewater in high volume. An
estimation from World Bank states that textile industry contributes 17–20% of industrial
water pollution (banana pith juice as natural coagulant article). Man-made textile fiber is a
very popular industry in Malaysia especially in the East Coast of Peninsular Malaysia. The
hand-made batik is a traditional inherited industry especially for the Malays community.
Today, this industry has contributed to the economic growth, especially in the states of
Kelantan and Terengganu. Malaysia has produced close to 400 000 tons of man-made fibers
which consist of nylon, polyester filament, and staple in 2008(www.yarnsandfibers.com) [9].
Malaysia’s man-made fibers contributed to about 1.03% of the world’s production. Malaysia
was the fifteenth largest producer of textile fiber in 2008 and ninth largest in Asian region.
Malaysia’s textile industry had exports and imports valued at RM 10.8 billion (US$ 3.6
billion) and RM 6.6 billion (US$ 2.2 billion), respectively, in 2011 [10]. At the same time,
the huge amount of textile fibers produced by textile industry in Malaysia also post
significant effects to the environmental quality, especially with respect to the liquid effluent
(current status of textile industry ww in malaysia). In general, textile wastewater is fairly a
complex mixture that contains many polluting substances and is highly varying in its
characteristics. Textile wastewater is a combination of types of dyes used and additives such
as oxidizing agents, surfactants, salts, heavy metals, dispersing agents and fin having
compounds that are persistent and lethal. Disposal of such heavily polluted wastewater into
water bodies result in contamination of soil and water. It effects environment adversely
pollution (banana pith juice as natural coagulant article).

The methods of treatment of wastewater that have been developed are physical or physico-
chemical, chemical, biological, electrochemical methods and membrane techniques. Primary
treatment processes are used to reduce load on secondary and tertiary treatment. Biological
treatments are insufficient in removal of color of the wastewater. Use of natural organic
material like seeds, leaves and other parts of plants has been found effective in water and
wastewater treatment (banana pith juice as natural coagulant article). Coagulation is a
common process in the treatment of both industrial wastewater and surface water. Its
application includes the removal of dissolved chemical species and turbidity via the addition
of widely used chemical-based coagulants such as alum (AlCl3), ferric chloride (FeCl3),
polyaluminium chloride (PAC), and synthetic polymer. Nonetheless, many disadvantages are
associated with the usage of these coagulants such as relatively high procurement costs as
well as detrimental effects on human health and environment (hindawi article). Introducing
natural coagulant would be beneficial in terms of environment, cost effectiveness and
economic sustainability. In addition, natural coagulants are biodegradable and not harmful to
human health. A number of studies have been reported using natural polymers for the
treatment of various types of wastewater [11-18] (hibiscus article).

Banana is herbaceous plant of the genus Musa spp. of the family Musaceae. Banana is one of
the most widely grown tropical fruits because of its high food value and an important
addition to the diet. In Malaysia, the production of commercial varieties of banana has
increased by 24–27% over the decades giving an amount of 27,453 hectares in 2009 with
Johor, Pahang, and Sarawak as the largest banana-producing states [16]. The stem from
which the fruit bunches have been taken should be cut off because it will never again grow
fruit. The stem will be left abundantly in the plantation and normally will just rot or be used
as fertilizer. According to Namasivayam et al. [17], waste banana pith can be used effectively
as an adsorbent for the removal of 87% Rhodamine B from textiles wastewaters at pH 4.
Another research also on colour removal showed that the pith of banana stem can effectively
remove the direct red colour and acid brilliant blue from aqueous solution through adsorption.
The adsorption capacities were 5.92 and 4.42 mg dye per gram of pith for direct red and acid
brilliant blue, respectively [18] (hidawi article).

Hibiscus Sabdariffa (Roselle) is widely available in Malaysia and the production is about 240
tons yearly. This plant has been used widely for food and medical purpose. However, the
capsules containing the seeds are usually discarded as a waste and by-product after the
processing process [17]. Nutritional study of roselle shows that the seeds are found to have
highest protein content compared with the flower and calyces which is 31.02 % and the seed
could be used as a potential source of proteins [18-21]. In addition, high amount of glutamic
acid and arginine (21.10 g/100 g protein and 11.35 g/100 g protein) present in the protein
from the seed of Roselle are expected to have the ability for coagulation [22]. Amino acids
which carry charges would give the overall charge to protein depending on the isoelectric
point. This protein is expected to be cationic that is able to neutralise the negative charged of
dye particle in dye wastewater (hibiscus sabdariffa article).
In the proposed study, the efficiency and performance of banana stem pith juice and roselle as
natural coagulant for the treatment of textile wastewater was analyzed. Parameters such as
pH, coagulant dosage and concentration of dye are also optimized using Response Surface
Methodology (RSM). Lastly both banana stem pith juice and hibiscus sabdariffa
performances are compared with conventional coagulant, aluminium sulphate (alum).

Lit review

Perspective on using coagulant in wwt

The particular impurities in wastewater are almost impossible to be removed without the
adding of coagulant agents. The understandable mechanisms of it makes coagulation as an
uncomplicated way for water purification since the 19th century (Choy et al. 2014; Jiang
2001). A lot of debates arise from researchers before regarding the mechanisms, proposing of
what it actually takes to work in the best conditions. According to Jiang (2001), the scientific
and depth study about coagulation starts approximately 100 years ago, after chemical
coagulants such as aluminium sulphate and ferric chloride have been used for water treatment
such in a big scale extensively. It is documented that the first proposed mechanism to explain
coagulation was from Schulze-Hardy rule, while the theory of particle collision function was
developed back in early 1917 (Jiang 2001). Early in 1940s, further studies were done towards
colloidal interaction, best known as van der Waals attraction but it was in 1960s when the
introduction of micro-electrophoresis started, for the next encyclopedic coagulation theory.
This led to the farther significant study of colloidal destabilization, by quantifying the zeta
potential on the colloidal particles itself. It is also recorded that the stoichiometric
relationship study between required coagulant dose to neutralize colloids and colloidal
particles concentration in coagulation treatment bloomed around this decade (Jiang 2001).
The usage of coagulants in wastewater’s physical-chemical treatment has even been recorded
since the earliest times, but using natural-based as the prime material. It was way foretime the
natural-based coagulants especially the one that extracted from plants were used as coagulant
for water clarification (Choy et al. 2014). For instance, Debora et al. (2013) stated that
natural-based coagulants were used since 4000 years ago with utilization of by nirmali
(Strychnos potatorum) in the countries such as India and Myanmar, while almonds and
soaked beans were practiced in Sudan and Egypt since 16th century as water purifying agents
to enhance water quality. The globalization era starts to take over the consumption of old and
aged treatment methods as sign of urbanization world, with massive technology and
advancing knowledge, left the traditional ways behind. Over the years, obvious gaps are
growing that differentiate the employment of natural and chemical coagulants. Both chemical
and natural-based coagulants have been effectively acknowledged in various ancient records
and past studies (Choy et al. 2014). However, it is sadly to be accepted that natural-based
coagulants are no longer the main priority with the invasion growth of more advanced
synthetic material, except the poor countries that have limitation in purchasing these goods.
Nonetheless, there is arising concerns regarding chemical coagulants thus make researchers
nowadays start to develop a more environmental friendly water and wastewater clarification
agent, likely from non-chemical based. Chemical coagulant agents such as polyaluminium
chloride and aluminium sulphate are among the most well-known and used in wastewater
treatment. They are used in coagulation which is primarily occupied to diminish the content
of impurities and organic matters that are devoting to water quality index (Zonoozi et al.
2011).

Need for natural coagulant

Chemical coagulant used has raised controversial issues due to its toxic nature for living
organisms and can be categorized into three types: hydrolyzing metallic salts, pre-
hydrolyzing metallic salts, and synthetic cationic polymers (Freitas et al., 2018; Verma et al.,
2012). Due to the low cost, easy handling, storage, and high availability, chemical coagulants
are more prevalent in wastewater treatment processes. Despite the availability, low cost etc.;
chemical coagulants are far behind in green chemistry due to high residual concentrations of
aluminum found in treated wastewater (Freitas et al., 2018; Matilainen et al., 2010).
According to Freitas et al., 2018; McLachlan 1995; Polizzi et al. 2002, Alzheimer’s disease is
linked with the neurotoxicity of aluminum. Synthetic polymer coagulants form hazardous
secondary products such as acrylamide which is carcinogenic and neurotoxic, and also
synthetic polymers have low biodegradability (Freitas et al., 2018; Kurniawan et al., 2020).
Excessive concentrations of chemical coagulants such as aluminum reduce the pH of water
tends and also, they can be accumulated to food chains (Kurniawan et al., 2020). Improper
disposal of toxic sludge pollutes the groundwater and soil. Accumulation of toxic sludge,
such as aluminum, iron etc., in natural water bodies causes adverse effects on aquatic
organisms and plant species (Kurniawan et al., 2020). Hence there is a need for the efficient
utilization of natural coagulants for water and wastewater treatment.

Pbc (effectiveness article) sama cam atas ni

Plant-based coagulants are generally derived from the various parts of the plants and are
organic, water-soluble, ionic, and non-ionic polymers in nature (Bodlund et al., 2014;
Dezfooli et al., 2016; Fatombi et al., 2013). In the colloid-free aqueous state and the colloidal
particle solution consisting of restricted irreversible loop arrangements, they maintain random
configurations and help in destabilization by forming micro or macro flocs through charge
neutralization (Hameed et al., 2016). Some plant-based materials may also behave as
flocculant by strengthening the flocs for better settleability (Al-Hamadani et al., 2011; Awang
and Aziz, 2012). Several works of literature have reported applying plant-based coagulants
for water and wastewater treatment (Kansal and Kumari, 2014; Kristianto, 2017; Oladoja et
al., 2017). Most of the investigated coagulants are from family Fabacea, primarily extracted
from the leaves (Rak et al., 2012) and seeds (Jayalakshmi et al., 2017). One of the most
popular and extensively researched plant-based coagulants is Moringa oleifera belonging to
the family Moringaceae (Baptista et al., 2017; Camacho et al., 2017). The other common
coagulants are Nirmali seeds, Tannins, Roselle seeds, Hyacinth bean etc, which have been
studied for turbidity reduction (Saharudin et al., 2014; Fermino et al., 2017; Choubey et al.,
2012). As in Table 3 is shown, they are low cost, non-toxic, locally available, readily
implementable, and show great potential. Plant-based coagulants are advantageous because i)
They are not dependent on chemicals; ii) they generate smaller amounts of sludge and
biodegradable; and (iii) less toxic and not corrosive (Rocha et al., 2019). Many wastewater
treatments have substituted chemical coagulants with plant-based coagulants because of their
low price, abundant source, multipurpose, and biodegradability (Othmani et al., 2020).

Future potential of natural material as commercial coagulant

In the perspective of natural coagulants, it is not impossible to develop them as commercial

ones based on the bright future potentials. Essentially, past studies have recorded that natural
material-based coagulants produce lesser volume of sludge (Altaher et al. 2016; Rasool et al.
2016), thus, convince the utilization of these alternative and possible choice of coagulants,
since it cut the cost of sludge treatment. The naturally occurring materials also highly
biodegradable (Awang & Aziz 2012; Birima et al. 2013; Rasool et al. 2016; Subramonian et
al. 2014), nonhazardous and toxic free (Rasool et al 2016; Rusdizal et al. 2015; Teixeira et al.
2017), differ than chemical-based that insecure the human health and cause environmental
hazards. Coagulants derived from natural materials can also be found in abundance especially
when it is plant-based and agro waste. The plants such as Moringa oleifera and rice starch can
be locally grown, where there is a lot of land space available (Rasool et al. 2016; Teixeira et
al. 2017). The thoughts in commercialization of natural materials as coagulants might also
boost the social factor of the locals that rely on these agricultural economy (Pondja et al.
2017; Yin 2010), also probably as solution towards wastewater and agro waste pollution. The
renewable sources of them also mean the continuous supply of raw materials in development
of coagulants. Therefore, the cheaper cost of coagulating agents could be obtained in future in
attempt to replace the hazards of using inorganic metal salts (Altaher et al. 2016; Yin 2010).
Fundamentally, the utilization of plant-based coagulants during early years also initiates
further researches regarding the potential natural materials to be developed as coagulants
(Awang & Aziz 2012; Birima et al. 2013; Subramonian et al. 2014). (Aishah article)

limitation of using natural material as commercial coagulant

few constraints also could be seen in commercializing the coagulants derived from these
biobased. A study by Choy et al. (2014) stated few distinct hinder factors that have the
tendency in failing the growth of natural materials into profit-making products, which are
financial source, research and development, and market awareness. Basically, the potential
investors are likely having doubts in investing in new products, lead to the limited financial
supply. The depth study of new knowledge is also the key for further development in
researches, so its certify factors such as strength and weakness can be identified. Awareness
regarding natural materials also needs to move simultaneously to seek for demands in
replacing the synthetic-inorganic coagulants. Besides, the working conditions of it to earn
optimal achievements might be questioned. Next, the accurate target market must be aimed to
the achieve practicability of both suppliers and consumers. While Altaher et al. (2016) and
Choy et al. (2014) mentioned that natural polymers could emerge the poor performance when
it is used as sole coagulants in remediating turbid wastewater. The after treatment might
resulted in immense concentrations of organic matter, thus worsen the turbidity level. The
identification of this problem can be tackled by accentuating the merge of natural and
chemical coagulants, either in the same or different treatment. The convincing coagulation
performance of combined coagulants will likely to improve treatment performance and
reduce the ratio of chemical coagulant as well (Rasool et al. 2016). The combined coagulants
can work either as coagulant aid or composite coagulant (Shak & Wu 2015). (Aishah article)
methodology

3.1 Preparation of coagulant from banana and roselle

Preparation of banana stem pith juice

Matured banana plants were collected from Raub, Pahang. The thorns were removed and the
pith of the stem was then separated from the foliage. 100 g of small pieces of the pith were
mixed with 10 mL of distilled water using a mixer. The mixed pith was then filtered and the
juice was collected. The fresh juice of banana stem was stored in a refrigerator at 7°C to
ensure its freshness. To avoid any fermentation, the coagulation experiments using this
banana stem juice as a natural coagulant were carried out on the same day.

Preparation of roselle seeds

Hibiscus Sabdariffa was obtained from Raub, Pahang. The seed bub was removed and the
good quality seeds were washed with water and dried at 60 ± 2 oC for 2 hours in an oven
[23]. The dried seeds were then pulverised using a grinder into powder form and was used for
each experiment. 5 g of seed powder was mixed with 100 ml of solvent which were distilled
water, 0.5 M sodium chloride (NaCl) and 0.05 M sodium hydroxide (NaOH) to extract its
coagulant agent. The extraction was done by using a household food blender for 2 minutes.
These solvents were chosen based on previous researches [10,11]. The coagulant was filtered
through muslin cloth to remove impurities and used in the subsequent jar test. In order to
prevent microbial decomposition of organic compound present in the coagulant, the
coagulant was prepared and used on the same day for optimum performance.

3.2 Preparation of synthetic dye wastewater

Stock solution of synthetic dye wastewater was prepared by dissolving accurately weighed
Congo Red (C32H22N6Na2O6S2; molecular weight: 696.66 g/mol) in distilled water to
concentration of 1000 ppm. The stock solution was diluted with distilled water to achieve
different concentrations of dye wastewater. The pH of the wastewater was adjusted using
concentrated hydrochloric acid (95 %) or 1.0 M sodium hydroxide (NaOH) to the desired pH
value.

3.3 Coagulation jar test

The coagulation process was performed to evaluate the performance of natural coagulant
using jar test. 500 ml of dye wastewater was added with coagulant and the mixture was
mixed for 4 minutes at 100 rpm for rapid mixing enhance floc formation. The sample was
stirred at 40 rpm to allow flocculation for 25 minutes and then settle for 30 minutes. The
colour removal after the coagulation was measured using a UV-Spectrophotometer (Model
HALO RB-10-5110026) with wavelength of 500 nm

3.4 RSM

Optimisation of working condition for banana stem pith juice and roselle seeds as a natural
coagulant was carried out using Response Surface Methodology (RSM). RSM is a popular
and economical statistical technique in evaluating the influence of parameters on treatment
response [24]. Three-factors and three level Box-Behnken response surface design (BBD)
was employed in this work. The variables and the level selected are given in Table 1. Colour
removal was analysed as the response.

Table ?: Experimental factors and levels of independent variables

3.5 Comparison of banana stem pith juice and roselle seeds with aluminium sulphate

Optimum combination of parameters was generated from RSM and jar test was performed for
both natural and chemical based coagulant with the optimised working condition. In this
study, aluminium sulphate (alum) was compared as chemical based coagulant as it is widely
used in conventional water and wastewater treatment. The results would indicate the ability
of natural coagulant to treat dye wastewater over chemical based coagulant.
SLIDE

INTRO

Textile manufacturing is a large and vital industry that utilizes textile auxiliaries, dyes, and
chemicals in its processes. Textile production processes generate a large amount of
wastewater due to the use of dyes, chemicals, and other additives. These operations consume
a large amount of water, resulting in the production of large amounts of wastewater.
According to the World Bank, the textile sector contributes between 17 and 20% of industrial
water pollution.

Man-made textile fiber is a very prominent sector in Malaysia, particularly on Peninsular

Malaysia's East Coast. In 2008, Malaysia produced over 400 000 tonnes of man-made fibers,
including nylon, polyester filament, and staple (YnFx, 2020).. Malaysia was the fifteenth
largest textile fiber producer in 2008 and the ninth largest in the Asia-Pacific region.

Textile wastewater is a mixture of dye types and additives such as oxidizing agents,
surfactants, salts, heavy metals, dispersion agents, and fin-containing chemicals. Disposal of
such highly polluted effluent into bodies of water results in soil and water contamination. It
has a detrimental influence on the environment through contamination.

Coagulation is a procedure that is frequently used in the treatment of industrial wastewater as

well as surface water. It is used to remove dissolved chemical species and turbidity by adding
chemical coagulants such as alum (AlCl3), ferric chloride (FeCl3), polyaluminium chloride
(PAC), and synthetic polymer. Nonetheless, there are numerous downsides to using these
coagulants, including extremely high procurement costs and adverse impacts on human
health and the environment (Alwi et al., 2013). Natural coagulant introduction would benefit
the environment, cost effectiveness, and economic sustainability. Furthermore, natural
coagulants are biodegradable and non-toxic to humans.

Banana is a herbaceous plant belonging to the genus Musa spp. in the Musaceae family.
Bananas are one of the most extensively farmed tropical fruits due to their great nutritional
value and importance to the diet. In Malaysia, commercial banana production has climbed by
24–27% over the decades, reaching 27,453 hectares in 2009, with Johor, Pahang, and
Sarawak producing the most bananas (Alwi et al., 2013). waste banana pith may be
successfully utilized as an adsorbent to remove 87 percent Rhodamine B from textile
wastewaters with a pH of 4. Another study on colour removal discovered that the pith of
banana stems can successfully adsorb the direct red and acid bright blue colours from
aqueous solution. Direct red and acid brilliant blue had adsorption capabilities of 5.92 and
4.42 mg dye per gramme of pith, respectively.

Hibiscus Sabdariffa (Roselle) is readily available in Malaysia, where it is produced in

quantities of approximately 240 tonnes per year. This plant has been widely used for culinary
and medicinal purposes. However, following processing, the capsules containing the seeds
are typically thrown as waste and by-products. the presence of a high concentration of
glutamic acid and arginine (21.10 g/100 g protein and 11.35 g/100 g protein, respectively) in
the protein from the seed of Roselle is likely to provide coagulation capacity (Tounkara et al.,
2013). Charged amino acids contribute to the overall charge of the protein, depending on its
isoelectric point. This protein should be cationic in nature and capable of neutralizing the
negatively charged dye particles seen in dye effluent.

LIT REVIEW

Without the addition of coagulant agents, the specific contaminants in wastewater are nearly
hard to eliminate. Coagulation has been used as a simple method of water filtration since the
nineteenth century due to its easily understood mechanics. Coagulants have been used in the
physical-chemical treatment of wastewater since the dawn of time, but with natural materials
as the primary component. Historically, natural-based coagulants, particularly those produced
from plants, were used to clarify water. worries about chemical coagulants have prompted
researchers to begin developing a more environmentally friendly water and wastewater
clarifying agent, most likely non-chemical in nature. Chemical coagulants such as
polyaluminium chloride and aluminium sulphate are well-known and widely utilized in
wastewater treatment. They are utilised in coagulation, which is primarily concerned with
reducing the amounts of pollutants and organic materials in water.

Chemical coagulants are more widespread in wastewater treatment procedures due to their
low cost, ease of handling, storage, and availability. Despite their availability, low cost, and
other advantages, chemical coagulants lag behind in terms of green chemistry due to the
significant residual aluminium concentrations found in treated wastewater. Coagulants
derived from synthetic polymers produce dangerous secondary products such as acrylamide,
which is carcinogenic and neurotoxic, and they also have a low biodegradability. Excessive
amounts of chemical coagulants, such as aluminium, tend to lower the pH of water and can
also accumulate in food chains. When toxic sludge is improperly disposed of, it contaminates
the groundwater and soil. The accumulation of hazardous sludge such as aluminium, iron,
and others in natural bodies of water has a detrimental effect on aquatic life and plant species.

Coagulants originating from plants are often organic, water-soluble, ionic, or non-ionic
polymers in nature. The majority of coagulants examined are from the Fabaceae family and
are derived predominantly from the leaves (Rak et al., 2012) and seeds (Jayalakshmi et al.,
2017). Moringa oleifera, a member of the Moringaceae family, is one of the most prominent
and thoroughly researched plant-based coagulants (Baptista et al., 2017; Camacho et al.,
2017). Other coagulants that have been researched for turbidity reduction include Nirmali
seeds, Tannins, Roselle seeds, and Hyacinth bean. They are low-cost, non-toxic, obtainable
locally, and offer promising results. Plant-based coagulants are also favourable because they
are chemical-free, produce less sludge, biodegradable and noncorrosive (Rocha et al., 2019).
Numerous wastewater treatment plants have shifted away from chemical coagulants in favour
of plant-based coagulants due to their low cost, abundant source, versatility, and
biodegradability.

previous research has demonstrated that natural material-based coagulants generate less
sludge = reduce sludge treatment cost. Natural materials are also highly biodegradable, non-
hazardous, and toxic-free. Coagulants originating from natural materials are also abundant,
particularly when it comes to plant-based and agricultural waste. Locally cultivated plants
such as Moringa oleifera and rice starch can be grown in areas with plenty of available land.
Commercialization of natural materials as coagulants has the potential to increase the social
factor of the native people who rely on these agricultural economies (Pondja et al. 2017; Yin
2010), as well as serve as a remedy to wastewater and agricultural waste pollution. Thus, a
lower cost for coagulating agents may be acquired in the future in an attempt to mitigate the
risks associated with the use of inorganic metal salts.

5
Identified several significant impediments to the growth of natural materials into profit-
generating goods, including financial resources, research and development, and market
awareness. potential investors are likely to have reservations about investing in new products,
resulting in a finite cash supply. The in-depth examination of new knowledge is also
necessary for ongoing progress in research, as it enables the identification of certifying
variables such as advantages and disadvantages. Concurrently, awareness of natural materials
must grow in order to generate demand for natural coagulants to replace synthetic-inorganic
coagulants. Additionally, the working conditions in which it operates in order to produce best
results may be questioned. Following that, a precise target market must be determined in
order to ensure the viability of both suppliers and customers. While Altaher et al. (2016) and
Choy et al. (2014) both said that natural polymers may exhibit poor performance when
utilized as the sole coagulant in turbid wastewater remediation. Following treatment,
enormous amounts of organic waste may develop, hence worsening the turbidity level. This
issue can be addressed by emphasizing the combination of natural and artificial coagulants,
either in the same or separate treatment.

Method