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Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-018-3850-9

APPROPRIATE TECHNOLOGIES TO COMBAT WATER POLLUTION

Utilization of extracts of Musa paradisica (banana) peels and Dolichos


lablab (Indian bean) seeds as low-cost natural coagulants for turbidity
removal from water
Achlesh Daverey 1 & Nisha Tiwari 1 & Kasturi Dutta 2

Received: 1 April 2018 / Accepted: 26 November 2018


# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
In this study, aqueous extracts of Musa paradisica (banana) peels and Dolichos lablab (Indian beans) seeds were prepared and
tested as natural coagulants for turbidity removal from simulated turbid water. Effects of extraction time (15, 30, and 45 min),
dosage (0.2 to 1.0 mL/L), and water pH on turbidity removals by the natural coagulants were evaluated. In both cases, the
extraction time of 45 min for the preparation of aqueous extract and dosage of 0.6 mL/L gave the best results in terms of turbidity
removal. Natural coagulants from M. paradisica peels powder could efficiently remove turbidity (> 83%) at all tested pH values
(3.0 to 12.0) with maximum turbidity removal of 98.14% at pH 11. In the case of D. lablab seeds, low turbidity removal (71–
74%) was observed at pH between 5.0 and 9.0. The maximum turbidity removal (98.84%) was obtained at pH 11. The scanning
electron microscopy (SEM) analysis of the settled flocs revealed that more compact flocs formed using M. paradisica peels
extract than those developed using D. lablab seeds extract. The chemical analysis and Fourier transform infrared (FTIR)
spectroscopy of the extracts revealed that polymeric substances (carbohydrate and proteins) having functional groups –OH,
C–N, C–C, –COOH, and N–H might be responsible for the coagulation activity. The zeta potential measurements of natural
coagulants revealed that the possible coagulation mechanism would be adsorption and bridging between particles. This study
demonstrated the potential use of aqueous extracts of M. paradisica peels and D. lablab seeds as low-cost natural coagulants for
turbidity removal.

Keywords Natural coagulants . Banana peels . Dolichos lablab . Sustainable water treatment . Turbidity removal

Introduction or synthetic organic polymer (e.g., polyacrylamide), although


capable of removing water turbidity, are not considered safe
Coagulation-flocculation is the method of choice for removal (Šćiban et al. 2009; Alwi et al. 2013; Choy et al. 2014;
of turbidity arising out of colloidal and suspended particles in Bouaouine et al. 2018). For example, drinking water contain-
water and wastewater treatment, where sedimentation or fil- ing aluminum residue from coagulants may cause
tration remains largely unsuccessful (Kashfi et al. 2018). Alzheimer’s disease and senile dementia in humans
Commonly used inorganic coagulants such as aluminum and (Rondeau et al. 2000; Walton 2013; Bondy 2016). Similarly,
iron salts (e.g., alum, Al2 (SO4)3, FeCl3, Fe (SO4)3) and their synthetic organic polymers have been reported to exert neu-
derivatives (e.g., poly aluminum chloride, poly ferric chloride) rotoxic and carcinogenic effects (Mallevialle et al. 1984;
Bratby 2006). In addition, the huge amount of toxic and
Responsible editor: Angeles Blanco non-biodegradable sludge from the use of chemical coagu-
lants needs further attention (Zemmouri et al. 2012;
* Achlesh Daverey Carvalho et al. 2016; Bouaouine et al. 2018).
ach15may@gmail.com; achlesh.senr@doonuniversity.ac.in Natural biodegradable coagulants are gaining immense in-
terest as non-toxic, a safe eco-friendly alternative to the prob-
1
School of Environment and Natural Resources, Doon University, lematic inorganic chemicals and synthetic polymers
Dehradun 248012, India (Asrafuzzaman et al. 2011; Swati and Govindan 2005).
2
Department of Biotechnology and Medical Engineering, National Local availability, low cost, milder treatment conditions
Institute of Technology, Rourkela, Odisha 769008, India (Maurya and Daverey 2018), high efficiency, and minimal
Environ Sci Pollut Res

sludge handling cost make natural coagulants as logical, sus- allowed to cool down to room temperature, and the developed
tainable choice for turbidity removal (Renault et al. 2009; color intensity was measured at 620 nm.
Nharingo and Moyo 2016; Bouaouine et al. 2018; Choy et al. The protein contents in the aqueous extracts were analyzed
2014). Various plant-based natural coagulants such as vegeta- by the standard Bradford assay using bovine serum albumin
bles, grains, and legumes have been studied for the turbidity standard (Bradford 1976). In brief, 10 μL of the sample (aque-
removal from water and wastewater (Choy et al. 2016; Kukić ous extract) was mixed with 1 mL of Bradford reagent, incu-
et al. 2015; Mohamed et al. 2015; Muthuraman and Sasikala bated for 5 min before taking absorbance at 595 nm. Fourier
2014; Ramavandi 2014). Some renewable materials such as transform infrared spectra (FTIR) of the powdered samples
orange peel, banana peel, banana pith, papaya seeds, and neem were obtained as KBr pallet with FTIR spectrometer (Perkin
leaf have also been tested (Maurya and Daverey 2018; Kakoi Elmer®, Spectrum Two). FTIR of the aqueous extracts was
et al. 2016). However, difficulties in preparation and/or pro- obtained as KBr pallet with Thermo Nikolet Nexus FTIR
cessing of natural coagulants possess a major hurdle to be ad- spectrometer. The zeta potential of aqueous extracts was mea-
dressed before their successful commercialization. Therefore, sured at different pH (3.0–12.0) using water as solvent by
exploration and extrapolation of simple preparation/extract Zetasizer (Nano-ZS, Malvern, UK).
methods for natural coagulants are highly desirable.
The aims of this study were to prepare natural coagulants Preparation of simulated turbid water
from Musa paradisica (banana) peels and seeds of Dolichos
lablab (Indian bean) by simple method, characterize the pre- Simulated turbid water, to test the potential of the prepared
pared natural coagulant, and evaluate the effects of process natural coagulants, was prepared in the laboratory as reported
parameters (extraction time of natural coagulant, water pH, co- by Kukić et al. (2015). In brief, kaolin powder (1% w/v) was
agulant dosage, and settling time of flocs) on turbidity removal. suspended in tap water and stirred for 2 h in a magnetic stirrer.
To the best of our knowledge, this is the first report on testing The suspension was kept undisturbed for 24 h to achieve
the aqueous extract of M. paradisica peels as natural coagulant. complete hydration of kaolin. This kaolin suspension was kept
in a refrigerator until use. Simulated turbid water was prepared
by 5× dilution of kaolin suspension in tap water. The turbidity
Materials and methods of this simulated turbid water, prepared just before the jar test,
was ~ 62 NTU.
Preparation of natural coagulants
Turbidity removal by natural coagulants
The peels of M. paradisica were collected from the Doon
University Hostel Mess, while the seeds of D. lablab were Experiments on turbidity removal by aqueous extracts of M.
purchased from local market, Dehradun, India. The natural paradisica peels and D. lablab seeds were performed using a
coagulants from the samples were extracted in distilled water six-paddle laboratory scale jar test apparatus (Microteknik,
as described by Kukić et al. (2015), with minor modifications. India). All the experiments were conducted in 1000 mL beakers
The banana peel was sun-dried for a week, followed by oven using 500 mL of simulated turbid water with a predefined dos-
drying at 60 °C for 20 min, before ground to fine powder age of aqueous extracts of M. paradisica peels and D. lablab
using a mortar pestle. The powder (1 g) was suspended in seeds. The suspension was rapidly stirred for 2 min at 150 rpm,
100 mL of distilled water, stirred for 15–45 min on a magnetic followed by a gentle agitation at ~ 80 rpm for 20 min to promote
stirrer at room temperature, and then filtered to obtain aqueous the flocs formation. The mixing was stopped and after 60 min of
extracts of M. paradisica peels. The seeds of D. lablab were settling time (if not specified), the supernatant was collected and
ground to fine powder, and the aqueous extract was prepared its turbidity was measured. The settled flocs were also collected
in a manner similar to that of M. paradisica. Both the extracts and characterized under a scanning electron microscope.
were stored in a refrigerator until use. All the experiments were performed in duplicate and con-
ducted at room temperature. Three sets of experiments (in
Characterization of natural coagulants duplicates) were performed for each coagulant. In the first
set of experiments, effects of extraction time (15, 30, and
The pH and turbidity of the prepared aqueous extracts were 45 min) of active coagulant and dosage (0.2 to 1.0 mL/L) on
analyzed by pH meter and turbidity meter, respectively. The the turbidity removal were evaluated. Effects of initial pH (3.0
total carbohydrate content was analyzed by the anthrone to 12.0) of simulated turbid water and flocs setting time (15 to
method using a glucose standard (Scott and Melvin 1953). 60 min) during jar test on turbidity removals were studied in
In brief, 1 mL sample was taken in a test tube and 4 mL the second and third sets of experiments, respectively. An
anthrone reagent (ice cold) was mixed with it. The mixture extraction time of 45 min and 0.6 mL/L of coagulant dosage
was boiled for 15 min at 100 °C in a water bath. Samples were were kept on hold in the second and third sets of experiments.
Environ Sci Pollut Res

Results and discussion

Characteristics of aqueous extract of M. paradisica


peels and D. lablab seeds

Physicochemical properties of natural coagulants

Table 1 shows the physicochemical properties of the natural


coagulants extracted from the M. paradisica peels and D.
lablab seeds. The extracts had near neutral pH with turbidity
< 6.0 NTU. Water as a solvent could extract the polymeric
substances (carbohydrates and proteins) from the M.
paradisica peels and D. lablab seeds. The extraction time
had a positive impact on the extraction of total carbohydrate
and proteins from the M. paradisica peels and D. lablab seeds.
The total carbohydrate and protein contents after 45 min of
aqueous extraction for M. paradisica peels (26.5 mg/L and
38.5 mg/L, respectively) were much higher than those of the
D. lablab seeds (9.2 mg/L and 29 mg/L, respectively). This
could have been the major reason for better turbidity removal
efficiency of M. paradisica peels extract. The difference in
protein/total carbohydrate ratio between M. paradisica peels
extract (1.45) and D. lablab seeds extract (3.15) suggests im-
portance of both proteins and carbohydrates residues in coag-
ulation process, but possibly in a complementary fashion.
Fig. 1 FTIR spectra of a powdered samples and b aqueous extracts of M.
paradisica peels and D. lablab seeds
FTIR analysis of natural coagulants
stretching of carboxylic acid, the C–C bond of diene
FTIR analysis of M. paradisica peels and D. lablab seed pow- and N–H deformation of amine, respectively (Kamel
ders and their aqueous extracts were performed to understand et al. 2017). Several peaks between 1600 cm−1 and
the functional groups involved in the coagulation process. The 950 cm−1 are attributed to the presence of polymeric
FTIR spectra of powdered samples of M. paradisica peels and substances such as ester, polysaccharide, and proteins.
D. lablab seeds are quite similar as both shows multiple trans- All these functional groups indicate the presence of
mittance peaks at different frequencies (Fig. 1a). A broad peak polymeric substances such as carbohydrates and protein.
from 3600 to 2800 cm−1 is attributed due to a free hydroxyl The FTIR spectra of aqueous extracts (Fig. 1b) show a
group, indicating the presence of polymeric compounds relatively fewer peak than their powdered counterparts. Key
(Deshmukh et al. 2017). A sharp peak at around 2926 cm−1 functional groups present in the extracts were a free hydroxyl
is attributed due to the C–H stretching of either alkane (Kamel group (broad peak from 3600 to 2800 cm−1), the C–C bond of
et al. 2017) or carboxylic acid (El-Din et al. 2017). A small diene (1635 cm−1) and the C–N bond of aliphatic amines
peak at 2851 cm−1 in M. paradisica peels powder is attributed (1107 cm−1). The presence of ester, polysaccharide, and pro-
due to COO− anion stretching (Memon et al. 2008). The teins in the extracts is confirmed by few peaks between 1600
peak at 1723, 1635, and 879 cm−1 is due to the C–O and 950 cm−1. The FTIR results further confirmed the results

Table 1 Characteristics of
prepared natural coagulants Parameter Aqueous extract of M. paradisica peels Aqueous extract of D. lablab seeds

Color Yellowish Whitish


pH 6.59 7.47
Turbidity (NTU) 5.8 NTU 5.4 NTU
Total carbohydrate (mg/L) 13.1a, 25.33b, 26.5c 7.1a, 8.83b, 9.2c
Proteins (mg/L) 23.5a, 33.5b, 38.5c 15a, 21.5b, 29c
a
Extraction time, 15 min; b Extraction time, 30 min; c Extraction time, 45 min
Environ Sci Pollut Res

Fig. 2 Zeta potential of natural coagulants from M. paradisica peels and Fig. 4 Effect of initial pH of water on turbidity removal efficiency of
D. lablab seeds as a function of pH selected natural coagulants

of chemical analysis indicating the presence of carbohydrates Zeta potential of natural coagulants and their possible
and proteins in the extracts. mechanism

The zeta potentials of natural coagulants at different pH values


are shown in Fig. 2. The zeta potential of natural coagulants
from M. paradisica peel was negative at all the tested pH
values and it varied from − 14.60 (pH 4.0) to − 37.60 mV
(pH 11). On the other hand, zeta potential of natural coagu-
lants from D. lablab seeds was + 2.39 mV at pH 3.0 and it
sharply decreased to − 33.70 mV at pH 7.0. The isoelectric
point (point of zero charge) of natural coagulants from D.
lablab seeds would be between pH 2.0 and 3.0. The zeta
potential of kaolin water is more negative (− 25 mV at
pH 3.0 and − 42 mV at pH 11.0; Yukselen and Kaya 2003)
than natural coagulants from M. paradisica peel and D. lablab
seed. These results indicate that the coagulation mechanisms
of the coagulants from M. paradisica peel and D. lablab seed
are unlikely to be charge neutralization. Adsorption and

Fig. 3 Effect of extraction time and dosage on turbidity removal using Fig. 5 Effect of flocs settling time in jar test experiments on the turbidity
aqueous extracts of a M. paradisica (banana) peels and b D. lablab seeds removal efficiency of selected natural coagulants
Environ Sci Pollut Res

Fig. 6 SEM images of settled


flocs using M. paradisica peels
extract as coagulant (left) and
using D. lablab seeds’ extract as
coagulant (right)

bridging between particles would be the most probable coag- experiments. Other natural coagulants (banana peels powder,
ulation mechanism of natural coagulants from M. paradisica papaya seed powder, neem leaf powder, banana stem juice,
peel and D. lablab seed. Similar zeta potentials and mecha- fava beans extracts, conventional starch) also showed negative
nism were reported in literature for the natural coagulants effects of high dosage (above optimum level) on turbidity
from Opuntia ficus-indica (Bouaouine et al. 2018). removal (Maurya and Daverey 2018; Kukić et al. 2015;
However, this is contradictory to the most widely used Choy et al. 2016).
coagulants—proteins from the seeds of Moringa oleifera
(Ndabigengesere et al. 1995) and alum (Subramonian et al. Effect of pH on turbidity removal
2014), whose coagulation mechanism is based on charge
neutralization. The pH is an important parameter in the coagulation process
as it can change the surface charge of the coagulant and/or
Effect of extraction time and dosage on turbidity pollutant (Kukić et al. 2015). Therefore, the effect of water pH
removal (3.0 to 12.0) on turbidity removals by aqueous extracts of M.
paradisica peel powder and D. lablab seed powder was stud-
Turbidity removals by the natural coagulants, processed at ied. For a fixed coagulant dosage (0.6 mL/L), maximum tur-
different extraction time (15, 30, and 45 min) from the M. bidity removal by both the aqueous extracts of M. paradisica
paradisica peel powder and D. lablab seed powder, were peel powder (98.14%) and D. lablab seed powder (98.84%)
studied at various dosages. The results, as shown in Fig. 3, was observed at pH 11.0 (Fig. 4). Three distinct phases of pH
clearly suggests a positive effect of extraction time on turbid- dependency on turbidity removal with D. lablab seed powder
ity removal efficiency for both the natural coagulants. It is extract were evident. Appreciable turbidity removal (78–84%)
obvious that with increasing time, the extracts got enriched was noted below pH 5.0 (phase I), followed by low turbidity
with polymeric substances (i.e., carbohydrates and proteins) removal (71–79%) between pH 5.0 and 9.0 (phase II), while
primarily responsible for the turbidity removal (Table 1). excellent turbidity removals (86–98%) were observed in
As expected, the coagulant dosage significantly influenced phase III (pH > 9.0). However, the impact of water pH was
the turbidity removal efficiency (Fig. 3a, b). In case of 45 min not significant in the case of extracts of M. paradisica peel
of extraction time, turbidity removals increased with dosage powder, where turbidity removals were > 80% at all tested pH.
up to 0.6 mL/L. Beyond this dosage, turbidity removals were Contrasting reports of pH dependence have also been reported
slightly diminished in both cases. Therefore, 0.6 mL/L was in the literature. For example, pH dependency on coagulation
used as an optimum coagulant dosage in the rest of the activity was reported for horse chestnut and acorn as natural

Table 2 Cost comparison of alum


as commercial coagulant with Coagulant Market price of Required dosage Cost of coagulant
natural coagulants used in this coagulant (USD/kg) (kg/million L water) (USD/million L water)
study
Commercial coagulant (alum)1 1.52 to 3.453 1004 150–345
D. lablab seeds 2.84 6 284
M. paradisica peels – 6 –
1
Aluminum sulfate; 2 Kemcore, China; 3 Mindy Materials, USA; 4 Parmar et al. (2011)
Environ Sci Pollut Res

coagulants (Šćiban et al. 2009) but not with fava bean (Vicia the other hand, utilization of M. paradisica peels for the prep-
faba L.) seed extracts (Kukić et al. 2015). This indicates that aration of coagulant is beneficial as it is a waste material and
the natural coagulants from M. paradisica peel powder were would have negligible cost towards transportation, drying,
highly stable at a wide range of pH and can be used as a and grinding of peels. It is also important to note that the
coagulant for treating real water and wastewater samples. dosage of commercial coagulant is ~ 16 times higher than
natural coagulants (Table 2). This indicates that the use of
Effect of setting time on turbidity removal natural coagulants will generate ~ 16 times less sludge than
commercial coagulants to treat the same volume of water.
Settling of flocs formed due to the action of coagulants is an Therefore, the sludge handling cost can be lowered by replac-
important and last event of the coagulation-flocculation pro- ing the chemical coagulants with natural coagulants.
cess. A faster settling of flocs is desirable in the coagulation
process and indicates the efficiency of coagulant. Figure 5
shows the effect of settling time on the turbidity removal (co-
agulation efficiency) of aqueous extracts of M. paradisica peel
Conclusion
powder and D. lablab seed powder. As expected, the turbidity
The study revealed that water is a good solvent to extract
removal increased from 73.21 to 87.71% when settling time
active coagulants from M. paradisica peels and D. lablab
increased from 15 to 60 min for D. lablab seed’s coagulant.
seeds. Chemical analysis and FTIR analysis confirmed the
The maximum turbidity removal (95.13% and 87.71% by M.
presence of polymeric substances (carbohydrate and proteins).
paradisica peel powder and D. lablab seed powder, respec-
The functional groups –OH, C–N, C–C, –COOH, and N–H
tively) was observed at 60 min of settling time. The result
might involve in the coagulation process. Extraction time and
indicates that flocs formed by the coagulants from M.
dosage significantly affect the turbidity removal. The best re-
paradisica peel powder were settled faster than D. lablab seed
sults in terms of turbidity removal were obtained at 45 min of
powder.
extraction time and 0.6 mL/L of dosage. Natural coagulants
from M. paradisica peels are highly active at all tested pH (3
Morphology of flocs formed with natural coagulants
to 12). On the other hand, the best water pH for natural coag-
ulants from D. lablab seeds is either < 5 or > 9. The flocs
The surface of flocs formed after the jar test experiment was
formed by the coagulants from M. paradisica peels are denser
observed under the SEM to study their morphology. SEM
than coagulants from the D. lablab seeds. Overall, the study
images of flocs (Fig. 6) formed using M. paradisica peels
confirmed that aqueous extract of M. paradisica peels is better
extract (left) and D. lablab seeds extract (right) were of
coagulant than the aqueous extract of D. lablab seeds.
irregular-shape flakes. However, the flocs formed using M.
paradisica peels extract were more closely and firmly packed
Acknowledgments The authors would like to thank Mr. Ashis Ranjan
compared to that of D. lablab seed extract. The compact flocs Behera for zeta potential analysis.
may be desirable as they are easy to handle and separate. This
could be the reason for the faster settling of flocs formed by Compliance with ethical standards The authors have
the coagulants from M. paradisica peel powder. The morpho- followed the accepted principles of ethical and professional conduct.
logical studies of flocs further confirmed that the natural co- The work did not involve human participants and/or animals.
agulants extracted from M. paradisica peels are better than
Conflict of interest The authors declare that they have no conflict of
coagulants extracted from D. lablab seeds.
interest.

Comparative analysis of natural coagulants


with commercial coagulant (alum)
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