Heliyon: R. Venkataraghavan, R. Thiruchelvi, D. Sharmila
Heliyon: R. Venkataraghavan, R. Thiruchelvi, D. Sharmila
Heliyon: R. Venkataraghavan, R. Thiruchelvi, D. Sharmila
Heliyon
journal homepage: www.cell.com/heliyon
Research article
A R T I C L E I N F O A B S T R A C T
Keywords: Statistical optimization models were employed to optimize the adsorption of textile dye effluent onto Gracilaria
Gracilaria edulis edulis. Significant factors responsible for adsorption were determined using Plackett-Burman design (PBD) and
Plackett-Burman design were time, pH, and dye concentration. Box-Behnken (BB) design was used for further optimization. The predicted
Box-Behnken design
and the experimental values were found to be in good agreement, the coefficient of determination value 0.9935
Decolorization
Desorption
and adjusted coefficient of determination value 0.9818 indicated that the model was significant. The results of
Engineering predicted response optimization showed that maximum decolorization could be attained with time 131.51 min,
Materials science pH 7.48, and dye concentration 23.13%. The model was validated experimentally with 92.65% decolorization
Chemistry efficiency. The experiment was confirmed using Fourier transform infrared spectroscopy (FTIR), high-resolution
Environmental science scanning electron microscope coupled with energy dispersive X-ray analysis (HR-SEM-EDX), X-ray diffraction
spectrometry (XRD) and Brunauer-Emmett-Teller (BET) surface area and pore size analysis techniques. Desorption
studies at various pH (2–14) were performed and a maximum of 23% of the dye was recovered from the adsorbed
biomass.
1. Introduction human life and the ecosystem. The treatment of textile dye is difficult due
to the presence of detergents and other additives which make them into a
Environmental pollution is an alarming problem in developing complex structure and the effluent is resistant to light, oxygen, acids, and
countries. The textile industry is one of the largest and rapidly developing bases. The treatment of wastewater containing dyes is difficult since they
industries in the world. A dye is a colored substance used in many in- have complex aromatic molecular structures which make them more
dustries such as the textile industry, leather, cosmetics, paints, food, stable. The treatment of the effluent can be done by physical, chemical,
ceramics, construction wax, paper, etc. The environmental problem such and biological methods (Kabbout and Taha, 2014) such as electro-
as water and soil pollution are mainly due to the release of untreated chemical treatment like electro-reduction, electrolysis, chemical precip-
textile dyes from the industries, surface runoffs, and sewage leakage and itation, aeration, coagulation, advanced oxidation process using
overflows (Piai et al., 2020). The release of textile effluent from the hydrogen peroxide or ozone and UV light to produce OH free radicals
textile industry contains a complex mixture chemical, dyes, starch, de- scavengers, membrane filtration, nano-filtration using nano-sized mem-
tergents, heavy metals, biological oxygen demand (BOD), chemical ox- branes, aerobic biological treatment using anaerobic microorganisms
ygen demand (COD), and sulphates. The effluent from industries are and non-aerobic biological treatment (Dasgupta J et al., 2015). These
generally strong-smelling, hot, and colored due to the presence of toxic methods are complex in design, automatic, rapid, and high rates of ac-
chemicals (Ghaly et al., 2014; Harrelkas et al., 2009). The dyes and the curacy compared to decolorization using adsorption. The predominant
chemicals are released into water bodies which change the nature of the drawback is that these techniques are non-cost-effective, fouling of
water making them unfit for human use and agricultural purposes. It also membrane, high electricity cost, sludge formation, and health hazards
affects the plants and animals present in the water bodies by inhibiting are a matter of concern (Parmar and Shukla, 2018). The biological
the penetration of sunlight into the water stream. The main concern of method is eco-friendlier, non-labor-intensive, and requires low-cost in-
the textile industry is the release of highly toxic chemicals and the vestment and is easy to perform. This is accomplished by the use of dead
quantity of effluent into the environment causing serious damage to biomass of plants, bacteria, fungi, algae, and yeast (Vijayaraghavan et al.,
* Corresponding author.
E-mail address: thiruchelvi.se@velsuniv.ac.in (R. Thiruchelvi).
https://doi.org/10.1016/j.heliyon.2020.e05219
Received 11 January 2019; Received in revised form 28 June 2020; Accepted 8 October 2020
2405-8440/© 2020 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
2013). Biological treatment requires a large surface area, proper main- adsorbents, photocatalysts, electrochemical catalysts and ion exchangers
tenance, and operation. tailoring environmental applications with promising results (Iftekhar
Adsorption technique is a simple and effective way for the removal of et al., 2018; Kang et al., 2016; Sharma et al., 2018, 2019). Organic and
dye from wastewater. Biosorbent is employed to decolorize the bleaching synthetic dyes, heavy metals, pesticides, and polyphenols have been
colored water (Kabbout and Taha, 2014). Various natural adsorbents are remediated through polymers through the process of adsorption, pho-
cost-effective such as agricultural waste, cotton waste, rice husk, dead tocatalysis, and biological remediation (Dhiman et al., 2017; Haroon
algal, and fungal biomasses, activated charcoal, and clay that act as po- et al., 2018; Piai et al., 2020; Sui et al., 2016). Nanocomposites of anionic
tential biosorbents (da Cunha Oliveira, 2016; Romauld et al., 2019). surfactant sodium dodecyl sulphate-iron silico phosphate are efficient in
Apart from these adsorbents, agricultural wastes such as apricot stone, adsorbing cationic heavy metals and dyes from aqueous solutions
cauliflower leaves, fruit peels, coir pith, corn cobs, tree bark, straw, ash, because of their selective ion exchange capability and stability (Sharma
Eugenia umbelliflora, and Ficus carica are potentially used as important et al., 2017). Thus, adsorption is more efficient than other remediation
low-cost, naturally occurring, and renewable adsorbents (Dubey and methods.
Shiwani, 2012; Kharat, 2015). Sawdust, rise husk, sugarcane bagasse, Calcium oxide and calcium sulphate are some of the low-cost effective
pistachio shell, Araucaria angustifolia bark, pine needles, and bamboo chemical adsorbents used for the decolorization of dye effluent and
sawdust are examples of some agricultural waste biomass that have been heavy metals from aqueous solutions. However, the reusability is lower
reported against various synthetic dyes (Georgin et al., 2018; Giusto when compared to other natural adsorbents (Ramesh et al., 2017). Ad-
et al., 2017; Hammud et al., 2015; Zhang et al., 2015). Also, timber sorbents are immobilized using sodium alginate and calcium chloride
waste, fruit peels like orange, banana, lime, coir pith, coconut husk, tea and used for the adsorption process promoting their reusability (Bai and
cake waste, coffee waste, and seaweeds (Chen et al., 2011; Gupta and Abraham, 2003).
Nayak, 2012; Machado et al., 2011; Popoola, 2019). Agricultural wastes Rhodophyta (red algae) is an economically important species and
are rich in negatively charged functional groups like carboxyl and hy- edible algae. Red algae occur in salt and freshwater environment and
droxyl enabling them to adsorb cationic dyes and heavy metals from warmer conditions. Gracilaria edulis is a marine species that belongs to
aqueous solutions. Studies reported that pre-treatment using formalde- the class Florideophyceae and family Gracilarales. It contains a double
hyde and acids enhanced adsorption efficiency by increasing the surface cell wall and an outer layer that contains polysaccharide agarose and
pore size (Khan and Nazir, 2015). Chitosan is a polymer derived from agaropectin (da Cunha Oliveira, 2016). It is a rich source of carrageenan,
marine sources like brine shrimps, crabs, and terrestrial insects. Chitosan sulphates, glucose, and polyunsaturated fatty acids. Red algae have a
is a low-cost, non-toxic biosorbent possessing high adsorption affinity high content of protein and low concentration of phenol group. The algal
towards cationic dyes due to the presence of hydroxyl, amino, and cell wall contains functional groups such as carboxyl, hydroxyl, and
carboxyl functional groups. Adsorption in chitosan is achieved through sulphate groups which act as a binding site for the charged dyes (Crist et
protonation of the amino-functional group resulting in electrostatic al., 1981).
interaction between dye and chitosan (Vakili et al., 2014). Chitosan Biosorption of textile dye effluent is affected by diverse process pa-
nanocomposites are very versatile in the application in the field of rameters influencing the rate and efficiency of adsorption. It is manda-
biotechnology in targeted drug delivery and environmental applications tory to optimize the parameters for the effective degradation of dyes,
like heavy metal adsorption due to electrostatic interactions (Sharma especially at higher concentrations. These parameters include pH, tem-
et al., 2017). perature, dye concentration, biomass concentration, static-agitation, and
Chemically modified adsorbent like nitrogen-modified titanium di- time. The optimized parameters would definitely reduce the cost and the
oxide reported by Janus et al. (2008) is one of the promising adsorbents reaction time spent and increases the efficiency of biosorption (Priyad-
for the removal of dyes from aqueous solutions. The main pitfall is that harshini and Bakthavatsalam, 2016). Hence, it is, therefore, necessary to
the adsorbent is not cost-effective. Hydrogel-based adsorbents such as optimize the parameters to maximize the adsorption of dye on to the alga
cross-linked and uncross linked polyacrylic acid, super-adsorbent nano- species viz. Gracilaria edulis.
composite hydrogels that are of nanometer-scale are also potential ad- There are several methods for the optimization and modeling avail-
sorbents for removing dyes from aqueous solutions. They are rich in able from the ancient elementary model like one factorial at a time
functional groups on their surface like alcohol, amides, and carboxylic (OFAT) to composite and nexus statistical designs like Plackett-Burman
acids and are non-toxic, hydrophilic making them more stable. Nano- design (PBD), Box-Behnken design (BB), and Central Composite Design
composites of hydrogel and hydrocolloids such as nano synthesized agar, (CCD) (Amara and Salem, 2010; Silveira et al., 2015). The OFAT was the
alginate, carrageenan, chitin, gelatin, and starch are some of the poly- most used in the ancient days to optimize the factors. This method was
mers that have wide applications in environmental and medical appli- labor-intensive, time-consuming, and non-efficient due to interaction
cations (Sharma et al., 2018). However, they are not cost-effective and among the factors (Jo et al., 2008). Alternately, the statistical experi-
are tedious in preparation compared to algae-based adsorbents. More- ments could overcome the drawbacks associated with the (OFAT) and
over, their efficiency is much lower compared to other natural adsorbents reduce the error in deducing the effect and interaction between factors
(Hu et al., 2018). Zeolites and clays are abundant microporous hydrous (Suhaila et al., 2013). The Design of Experiments (DOE) propounds a
aluminosilicates mineral adsorbents used predominantly for the minimum number of experimental trials. The DOE increases the effi-
adsorption of heavy metals and dyes from aqueous solutions due to the ciency of any process (Sivasubramanian and Namasivayam, 2015). PBD
cationic and anionic electrostatic interactions between them (Ngulube and Response surface methodology (RSM) (BB and CCD) designs are the
et al., 2017; Wang and Peng, 2010). The high dispersive nature of clay most commonly used by the scientific communities for the process pa-
and zeolites makes reusability studies difficult (Xu et al., 2012). Smectite rameters optimization (Lakshmikandan et al., 2014; Agarry and Ogun-
rich clays, mesoporous zeolites, graphene oxide composites, mesoporous leye, 2012).
kaolin-based silica, magnesium phyllosilicates, and cellulose hydrogel Plackett Burman design is a very efficient method of screening to
are some of the natural clay and zeolite-based composites commonly identify the significant factors among a large number of factors that in-
used as adsorbents (Briao et al., 2018; Chaari et al., 2019; Li et al., 2015; fluence a process using a few experimental runs (Ungureanu et al., 2015).
Moscofian et al., 2012; Yang et al., 2019). Gum arabic, a natural polymer RSM has been used importantly in various sectors and industries like
composed of repetitive units of 1,3-linked β-D-galactopyranosyl has product development, food industries, and bio-processing industries like
versatile applications in environmental applications because since they bakeries and breweries through fermentation. RSM is an effective sta-
are cheaper, reusable, and highly efficient in remediation (Sharma et al., tistically designed methodology used to traverse the interactions be-
2018). Nanocomposites of biopolymers using silver, strontium, cerium, tween the independent variables and the dependent variables and predict
bi, and trimetallic and graphene oxides have been widely used as the resultant responses in the presence of defined conditions (Jabeen
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R. Venkataraghavan et al. Heliyon 6 (2020) e05219
et al., 2015). The BB design permits the calculation of the responses at effluent was characterized for physicochemical analysis at Tamil Nadu
intermediate levels that were not been studied experimentally. The testing labs, private limited, Chennai, and was reported in Table 1. The
three-level BB design was commissioned in this study and the parameters effluent was found to exceed the limits when compared to the Tamil
were optimized with the minimum number of experimental trails Nadu pollution control board's standards for waste effluent discharge.
compared to the other designs (Dong et al., 2009).
Therefore, the objective of the present research work was to obtain 2.3. Pretreatment of biomass
the significant parameters affecting the biosorption of textile dye effluent
on to Gracilaria edulis using PBD and further optimizing the responses to Pretreatment of the biomass was done to enhance the biosorption of
maximize the efficiency of the process using the BB design and charac- dye effluent on to the biomass. Physicochemical modifications of biomass
terize them using sophisticated instrumentation techniques. could lead to the activation of binding sites resulting in better sorption
uptake.
2. Materials and methods
2.3.1. Physical pretreatment method
All the chemicals used in this study were purchased from HiMedia Physical treatment of the biomass was done using boiling water. 30 g
laboratories and were of the highest purity. 0.1 N HCl and 0.1 M NaOH of powdered biomass was added to add to 800 mL of 150 C boiling water
were prepared to adjust the pH of the solution. and was stirred continuously for 15 min. Then the biomass was filtered
using Whatman filter paper (size 40) and a glass funnel to remove the
2.1. Collection, authentication and preparation of biomass water. The biomass was then dried in the hot air oven at 60 C for 24 h
(Zafar et al., 2013). Boiling water enhances the adsorption capacity of
The marine red macroalgae Gracilaria edulis was collected from the biomass by increasing the pore surface area.
shallow intertidal zone along the Mandapam coast (Latitude:
9 160 32.5600 N & Longitude: 79 70 25.0300 E), Ramanathapuram district, 2.3.2. Chemical method
Tamil Nadu. The confirmation and authentication of the species were
done by Dr. M. Ganesan, Senior Scientist, Council of Scientific and In- 2.3.2.1. Pretreatment using calcium chloride. 20 g of biomass was added
dustrial Research - Central Salt and Marine Chemicals Research Institute to 500 mL of 0.2 M calcium chloride and the pH was adjusted to 5. The
(CSIR-CSMCRI), Mandapam Camp, Tamil Nadu. The algae were washed mixture was then shaken in an orbital shaker at 150 rpm for 24 h at 25 C
initially with water to remove the epiphytes and other contaminants and overnight for effective ion-exchange and complete crosslinking of alginic
were packed in an air-tight polythene bag and was brought to the lab materials. The biomass was then washed with distilled water to remove
(Venkataraghavan and Thiruchelvi, 2019). Then the algae were washed traces of calcium chloride and dried in the hot air oven for drying at 60 C
with distilled water to remove the salts. The algae were shade dried for for 24 h (Hanbali et al., 2014; Batzias and Sidiras, 2004).
one week and crushed using mortar and pestle and further broken down
with the help of an electric blender into small pieces. The biomass was 2.3.2.2. Pretreatment using formaldehyde. 20 g of biomass was added to
sieved manually using a mesh sieve (size no: 18) to obtain a particle size 170 mL 36% formaldehyde and 330 mL of 0.1 N hydrochloric acid. The
of less than 1000 μm and stored in a clean dry place. mixture is shaken in orbital shaker for effective crosslinking and poly-
merization of alginic materials and was incubated in an orbital shaker at
2.2. Collection and characterization of textile dye effluent 150 rpm for 1 h. The biomass was then washed with distilled water to
remove traces of formaldehyde and hydrochloric acid. The biomass then
The textile dye effluent was obtained from a textile processing in- treated with 0.2 M Na2CO3 solution and again washed with distilled
dustry in Murugampalayam, Tiruppur, Tamil Nadu. The textile dye water. It was dried at 60 C for 12 h and at 110 C for 2 h (Leusch et al.,
effluent was dark green in color with foul smell due to the mixture of 1995).
several dyes like disperse dyes, direct dyes, cationic dyes, sulfur dyes,
anionic dyes, and azoic dyes. The dyes were collected from the exit 2.4. Experimentation
discharge of the industry. The effluent was stored in plastic bottles in a
dark place under normal room temperature. The dye was analyzed be- The optimization experiments were performed as batch adsorption
tween the ranges 800 to 200 nm spectrum in the (Shimadzu-1800) UV- studies in 250 mL Erlenmeyer flasks containing 100 mL of diluted dye
Vis spectrophotometer and λmax of the effluent was found to be 578.8 effluent. The dye was diluted appropriately to respective concentrations
nm. The effluent was diluted to 10% (v/v) (10 mL of crude dye in 90 mL using distilled water. The factor levels were maintained during the
of distilled water), 20% (v/v) (20 mL of crude dye in 80 mL of distilled experiment. The adsorption studies were performed in the incubator for
water), and 30% (v/v) (30 mL of crude dye in 70 mL of distilled water) static conditions and the orbital shaker for agitated conditions. Constant
using distilled water respectively and used for the experiment. The dye agitation speed of 150 rpm was maintained throughout the study. On
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R. Venkataraghavan et al. Heliyon 6 (2020) e05219
reaching equilibrium conditions, the effluent was centrifuged at 2500 which includes a coefficient of determination (R2), and its statistical
rpm (Remi R–8C Laboratory Centrifuge) for 5 min to remove the biomass significance was scrutinized by Fischer's test (F-test). The coefficient of
debris and the supernatant was preserved. The filtrate after each trial was determination (R2) was used to measure the goodness of fit of the model.
analyzed using (Shimadzu UV-1800) UV-Vis spectrophotometer at 578.8 The response contour and surface plots were studied. The contour and
nm with sterile distilled water as blank and the readings were tabulated. surface plots showed good interaction between the significant factors.
Effluent without adding biomass was used as control. The decolorization
percentage was calculated using the following equation (Eq. (1)).
2.6. Analysis of data
Y ¼ (Initial absorbance – Final absorbance /Initial absorbance) * 100 (1)
where Y denotes the decolorization percentage. Minitab18.1, Pennsylvania, U.S.A was used for the statistical and
regression analysis of data. This software is chosen since it provides a
very comprehensive and easy interpretation of results.
2.5. Design of experiments
2.5.1. Screening of process parameters using Placket-Burman design (PBD) 2.7. Characterization of biomass using fourier transform infrared
The PBD is an effective method used for screening the significant spectroscopy, scanning electron microscopy coupled with energy dispersive
factors from a large number of factors affecting the process (Zhou et al., X-ray analysis, X-ray diffraction spectrometry and Brunauer Emmett Teller
2011). The following first-order polynomial equation (Eq. (2)) was used surface area analysis
to perform mathematical modeling.
Fourier transform infrared spectroscopy (FTIR) was performed at
Y ¼ β þ Σ β xi
○ ○ (2) Sophisticated Instrumentation Facility, Vellore Institute of Technology,
where Y denotes the predicted response (decolorization percentage), β ○
Vellore. The spectra were analyzed by Thermo Electron Scientific using
denotes the model intercept, βi denotes the linear coefficient, and xi de- the KBr disc mode. The sample was mixed with 1% KBr and pressed into
notes the level of each independent variable. pellets and was analyzed in the mid-infrared region (400-4000 cm1) at 4
Six independent variables namely i) pH, ii) temperature, iii) dye cm1 resolution to obtain the spectra.
concentration, iv) biomass concentration, v) static-agitation, and vi) time A high-resolution scanning electron microscope (HR-SEM)
were investigated at 95% confidence level in a single replicate. The coupled with energy dispersive X-ray analysis (EDX) was used to
factors were varied according to the two-level PBD. PBD matrix was analyze the morphology of biomass before and after adsorption. The
developed for 6 parameters with 12 experimental trials to shortlist the analysis was performed at the Sophisticated Analytical Instruments
significant parameters that influence the biosorption by Gracilaria edulis Facility, Indian Institute of Technology, Madras using FEI Quanta 200
(El-Naggar et al., 2018; Ungureanu et al., 2015). Every independent FEG-EDAX high-resolution scanning electron microscope. The sam-
variable was assessed at lower (-) and higher (þ) levels (Table 2). ples were made electrically conducting by coating a layer of gold on
Table 3 denotes the experimental design (factors and range) of the their surface. The analysis after biosorption was carried out for the
biosorption process using PBD. The factors having P-value lesser than third trial of Box-Behnken design since it has the highest biosorption
0.05 (confidence level greater than 95%) were considered to be signifi- efficiency (Table 7).
cant and thus influence the decolorization process. The significant factors X-ray diffraction spectrometry (XRD) was performed at Central
were further optimized using the Box-Behnken design of RSM. Instrumentation Facility, Vels Institute of Science, Technology and
Advanced Studies, Pallavaram. XRD was used to analyse the crystalline,
2.5.2. Response surface methodology (RSM) using Box-Behnken design amorphous nature, and mineral content of biomass (Zhou et al., 2018).
(BB) of experiments The analysis was carried using Rigaku Smart Lab X-ray diffractometer
Once after screening the significant factors using PBD, the RSM using using Cu-Kα radiation source, λ ¼ 0.15406 Å at 45 kV and 40 mA in the
the BB design was performed to obtain the details regarding the signifi- 2θ range of 0–100 . The XRD data was compared with Mineralogy
cant effects and to study the interactions between the shortlisted signif- Database to identify the mineral composition (Table 9). The average
icant factors with a positive effect on the decolorization of the dye crystallite size was calculated using the Debye-Scherrer equation (Holz-
effluent and to determine the optimal value of every variable that would warth and Gibson, 2011).
influence the decolorization of dye to the maximum. Brunauer Emmett Teller (BET) and Barrett-Joyner-Halenda (BJH)
Three factors were found to be significant from the PBD: i) time for surface area and pore size analysis were performed at Central
(minutes), ii) pH and iii) dye concentration (%) and were further opti- Instrumentation Facility, Vels Institute of Science, Technology and
mized using BB design. Each significant factor or independent variable Advanced Studies, Pallavaram using BELSORP-max analyzer. The
was evaluated at three disparate levels: center points (-, 0, þ) (Table 4). analysis was performed at low pressure (1*108) using inert nitrogen
The decolorization of dye effluent was investigated using the second- at 77K and argon at 87K using a 13.3 Pa pressure transducer. The
order polynomial equation. The data were fitted on to the second-order biosorbent was analyzed before and after adsorption to study the
equation by multiple regression method. The following second-order total surface area, total pore volume, and mean pore diameter.
quadratic equation was used (Eq. (3)). Adsorption-desorption isotherm and pore size distribution were
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R. Venkataraghavan et al. Heliyon 6 (2020) e05219
Table 3. Experimental design of factors with experimental and predicted results using Plackett-Burman Design.
Experimental Predicted
1 þ - þ - - - 90.72 90.78
2 þ þ - þ - - 88.40 88.42
3 - þ þ - þ - 92.54 92.75
4 þ - þ þ - þ 87.23 87.48
5 þ þ - þ þ - 88.65 88.62
6 þ þ þ - þ þ 88.05 87.80
7 - þ þ þ - þ 89.64 89.25
8 - - þ þ þ - 92.53 92.64
9 - - - þ þ þ 88.45 88.47
10 þ - - - þ þ 86.89 86.82
11 - þ - - - þ 87.95 88.37
12 - - - - - - 91.94 91.56
Factors Coded levels where Y in Eq. (4) is the response (decolorization percentage). Table 5
- 0 þ denotes information about significant factors (P < 0.05). The value of the
Time 120 150 180
coefficient of determination (R2) was found to be 0.9852 which indicated
that 98.52% of variability could be explained by the selected model and
pH 3 6 9
could not explain only 1.48% of the total variability. Moreover, the
Dye concentration 10 20 30
predicted R2 value of 0.9146 was found to be an inequitable agreement
with the adjusted R2 value of 0.9674 which denotes the validity of the
plotted using inert gases under a vacuum environment, the saturated model.
vapor pressure of 102.72 kPa conditions. Table 6 shows the information about statistical analysis of experi-
mental data using Fischer's test for Analysis of variance and provides
3. Results and discussion detailed information about the T-values and P-values for each indepen-
dent variable which served as tools to identify the significant factors
3.1. Selection of significant factors influencing the decolorization of textile affecting the process. The Model Fischer's value of 55.39 and the T-value
dye effluent using Plackett-Burman design (PBD) of 845.25 were obtained.
A decrease in decolorization was observed when the time (coeffi-
PBD is an effective screening design used to identify the significant cient value of -1.381) was increased from 120 to 180 min (- to þ). Other
factors affecting the decolorization of textile dye effluents from a large factors such as pH, temperature, and biomass concentration (coefficient
number of candidate factors. It is a two-level fractional factorial design and value of -1.093, -0.211, and -0.266) were also found to a exert negative
is based on the first-order polynomial equation without any interaction effect on the decolorization process. Thus, by decreasing the time, pH,
among the independent factors (Plackett et al., 1946; Jabeen et al., 2015). temperature, and biomass concentration were found to exert a positive
The influence of six important factors was statistically analyzed using effect on the dye decolorization process. On the other hand, the in-
the PBD. Three of the six factors namely i) time, ii) pH, and iii) dye crease in dye concentration and static-agitation (coefficient value of
concentration a have significant effect on the decolorization of the 0.702 and 0.103) had positive effect on the decolorization process.
effluent. The factors with P < 0.05 (confidence levels>95%) were Thus, by increasing the dye concentration could exert a positive effect
assumed to be significant and chosen for the next level of optimization by on the dye decolorization. The maximum response of 92.54% (experi-
the Box-Behnken (BB) design of RSM. Multiple regression analysis was mental) was obtained at pH 3; temperature 40 C; dye concentration
applied to the experimental results and fitted on to first-order polynomial 30%; biomass concentration 1 g/L; agitated condition; and time 120
equation represented as Y. min in the third trial of PBD (Table 3).
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R. Venkataraghavan et al. Heliyon 6 (2020) e05219
DF- Degrees of Freedom; Adj SS- Adjusted Sum of Squares; Adj MS- Adjusted Mean Square.
3.2. Statistical process optimization of textile dye effluent decolorization by et al., 2010). Nevertheless, Koocheki et al. stated that higher values of R2
Gracilaria edulis using Box-Behnken (BB) design do not mean that the regression model is moral and, in that case, the
conclusion can be done depending upon a greater adjusted R2 value
Significant factors obtained from the PBD namely i) time, ii) pH, and Koocheki et al. (2009). The R2 value for the model was found to be
iii) dye concentration were further statistically optimized and studied 0.9935 and the adjusted R2 was 0.9818 which denoted a very good
using the three-level (-, 0, þ) BB design. The experiment was performed agreement between the experimental and the adjusted R2 values. The
in a single replicate. The levels of the factors were set based on the coefficient of determination (R2 ¼ 0.9935) indicated that 99.35% of
previous PBD. A matrix was designed with three variables containing decolorization variability could be explained by the model. Moreover,
coded and actual levels with their responses (decolorization percentage) the adjusted R2 value (0.9818) was also found to be high denoting a
were displayed in Table 7. Temperature, biomass concentration, and greater significance of the model. The predicted R2 value for the model
static-agitations exerted negative effect (insignificant factors) on the dye was found to be 0.8958 which was also very high. Additionally, for a
decolorization were set at their respective low levels of their PBD for model to be significant, the predicted R2 and the adjusted R2 values must
further optimization. The BB design presented fifteen trials with exper- be less than 20% (Rai et al., 2016). In the present study, the predicted R2
imental and predicted values for three factors (Table 7). Depending on ¼ 0.8958 was found to be in good agreement with the adjusted R2 value
the contrast in the three significant variables, the percentage of decol- of 0.9818 indicating the validity of the model and the model could
orization varied from 86.97% to 92.30% in the sixth and the third trials. explain 89.58% variability in predicting the decolorization of textile dye
The maximum decolorization potential was attained at the third trial effluent in the range of experimental variables. The regression co-
with 92.30% decolorization at time 120 min; pH 9; dye concentration efficients equation was calculated and the experimental data was suited
20% (Table 7). on to the second-order polynomial equation (Eq. (5)). The equation ob-
tained could describe the decolorization percentage.
3.3. Analysis of variance for box behnken design Y ¼ 65.29 þ 0.1825 Time þ 2.384 pH þ 0.5454 Dye conc – 0.000647 Time-
*Time – 0.1322 pH*pH – 0.02135 Dye conc*Dye conc – 0.00758 Time*pH þ
The analysis of variance of the model using second-order polynomial 0.001925 Time*Dye conc þ 0.02567 pH*Dye conc (5)
using BB design was tabulated (Table 8). According to Cui et al., a
where Y represent the predicted decolorization percentage.
regression model with R2 (coefficient of determination) value greater
From Eq. (5), the highest regression coefficient was achieved by pH
than 0.90 would possess a high correlation (Cui et al., 2010). The value of
(2.384), followed by dye concentration (0.5454), followed by time
R2 should not be lower than 0.74 until the model is appropriate (Le Man
Table 7. Experimental design of factors with experimental and predicted results using Box-Behnken Design.
Experimental Predicted
1 - - 0 89.65 89.62
2 þ - 0 89.60 89.87
3 - þ 0 92.30 92.02
4 þ þ 0 89.52 89.54
5 - 0 - 88.95 89.11
6 þ 0 - 86.97 86.84
7 - 0 þ 90.52 90.64
8 þ 0 þ 90.85 90.68
9 0 - - 87.77 87.62
10 0 þ - 87.02 87.12
11 0 - þ 88.87 88.76
12 0 þ þ 91.20 91.34
13 0 0 0 92.04 92.04
14 0 0 0 92.04 92.04
15 0 0 0 92.04 92.04
6
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
DF- Degrees of Freedom; Adj SS- Adjusted Sum of Squares; Adj MS- Adjusted Mean Square.
(0.1825). All the factors had a net positive regression coefficient indi- 3.4. Surface and contour plots- interaction between the significant factors
cating a positive effect on the dye decolorization. Table 8 denotes the
analysis of variance which is mandatory to analyze the adequacy and The two-dimensional contour and three-dimensional surface plot
significance of the experimental model (Harrelkas et al., 2009). Analysis were used to investigate the effect of the individual variables and their
of variance splits the total variation into two distinct components namely interaction for the predicted responses on the decolorization of dye
i) variation affiliated with the model and ii) variation affiliated with the effluent. Figures 1, 2, and 3 show the 2D contour and 3D surface plots.
experimental error. The results from the analysis of variance show The plots were based on Eq. (5) where one variable was kept constant and
whether the model was significant or not when correlated with the the other two variables were altered inside the experimental range. The
variations affiliated with the residual (difference between the experi- shape of the surface and its corresponding contour plot was important to
mental and the predicted) error (Aleboyeh et al., 2008). The F-value study the mutual interactions between the variables. Each response
gives the ratio between the mean square and the residual error of the surface plot (Figures 1, 2, and 3) denoted a clear peak in the center,
model. From Table 8, the F-value was found to be 84.77 and the which indicates that the optimum value point was within the experi-
lack-of-fit value was found to be 0.1001. F-ratio of the model was found mental boundary level.
to be 84.77 which is greater than the tabulated F-value (F ¼ 0.1001 at Figure 1 (a and b) shows the graphical representation indicating the
95% significance) indicating the adequacy of the model. The T-value and combined effects of pH and time on dye decolorization while the dye
the P-value were used as predominant tools used to evaluate the signif- concentration was set to its zero levels (Dye conc ¼ 20%). From Figure 1
icance of every coefficient. Thus, the linear, quadratic, and interactive (a and b), it was clear that an increase in the pH could augment the
terms were found to be highly significant for the textile dye decolorization of dye effluent (Y). The maximum decolorization was
decolorization. observed in the pH range 5.8–9. pH plays an important role in the
Figure 1. Contour plot and response surface plot showing interaction between time and pH.
7
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
Figure 2. Contour plot and response surface plot showing interaction between time and dye concentration.
Figure 3. Contour plot and response surface plot showing interaction between pH and dye concentration.
decolorization through biosorption due to the attraction of charged dyes Figure 3 (a and b) showed the interaction effects of dye concentration
onto the surface of the adsorbent. An increase in the concentration of Hþ and pH while the time was set at its zero levels (Time ¼ 150 min). A
ions (acidic) attracts anionic dyes while an increase in the concentration mutual increase in the dye concentration and pH could exert an
of OH ions (basic) attracts cationic dyes towards the biomass surface augmented efficiency in the decolorization of dye (Y). However, the
due to electrostatic force of attraction (Ashraf et al., 2006). A decrease in decolorization efficiency decreases over a prolonged increase in both
the decolorization efficiency was found when there was an increase in factors. This could be due to the saturation of the available binding sites
the time from 120 to 152 min. The response surface plot showed a clear on the biomass surface. The optimum dye concentration was found to be
peak and the corresponding contour plot showed a diagonally elongated between 19 to 25%, further increase causes a decrease in adsorption
uniform design implying that the interaction between the pH and time efficiency. On the other hand, an increase in the pH also played a vital
was significant on dye decolorization. role in the decolorization process. Accumulation of OH due to an in-
Figure 2 (a and b) shows the graphical representation indicating the crease in the pH 5.5 to 8.8 (acidic to basic) could be responsible influ-
combined effects of dye concentration and time on dye decolorization encing the binding of cationic dyes onto the surface of biomass (Ashraf
while the pH was set at its zero levels (pH ¼ 6). From the contour plot et al., 2006), hence a considerable increase in decolorization could be
Figure 2 (a and b), it was clear that the decolorization efficiency (Y) obtained. The response surface plot implied a dome shape and the cor-
increases with an increase in the dye concentration from 19 to 25% and responding contour plot indicated a dark green colored diagonally
reaches the maximum value and then decreases. The possible reason for elongated design implying that the interaction between the dye con-
the decrease in the decolorization efficiency could be due to the satu- centration and pH was significant on dye decolorization (Y). The opti-
ration of biomass. Saturation of biomass indicates that there were no mized values of the parameters could be found within these regions.
free binding sites available for adsorption of dye (Smaranda et al., The dye adsorption capacity is mainly influenced by the surface
2009). Maximum decolorization was attained within 162 min after morphology of the algae and the functional groups present on its surface
which a decrease in decolorization could be found. The response sur- and reactive sites present on dye molecules (Crist et al., 1981; Sharma
face plot showed a clear peak and the corresponding contour plot et al., 2018). The algal biomass was characterized using Fourier trans-
showed a diagonally elongated design denoting that there was a mutual form infrared spectrometry before and after adsorption of dye (Figure 4).
interaction between the dye concentration and time and was There were many significant differences observed after the dye adsorp-
significant. tion. Typically, the intensity of N–H and O–H bands at 3311.78 cm1
8
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
were decreased to 3282.84 cm1 denoting an influence of hydroxyl (Figure 5 (b)). Adsorption of dye on the surface of biomass is very clear
functional group and hydrogen bond that were involved in the adsorp- from Figure 5 (b) at 3,000X magnification. This could be possible due to
tion (Catherine et al., 2018; Du et al., 2014; Mohamed et al., 2019). The the electrostatic attraction between the functional groups on the biomass
peak at 1635.64 cm1 ascribed to C¼C functional group was decreased to and charge on the dye (Ashraf et al., 2006; Namasivayam et al., 2001).
1633.71 denoting the participation of π-π interactions in the dye uptake EDX was employed in the study to characterize the materials accumu-
(Dai et al., 2018). Typical CH3 and CH2 bands at 1454.33 and 1425.40 lated on the surface of biomass. Since there is a rapid increase in the
cm1 disappeared after dye adsorption onto biomass. Bands at 1249.87 industrialization, accumulation of pollutants and heavy metals have been
cm1 and 1149.57 responsible for aromatic ether and C–O was dis- found everywhere. These are a potential threat to humans and the
appeared after dye uptake. The interaction between the adsorbent and environment as they possess toxic, mutagenic, and teratogenic properties
adsorbate occurs due to three mechanisms namely electrostatic, (Roeva, 1996; Scimeca et al., 2017). EDX (Figure 6) showed the presence
hydrogen bond, and hydrophilic-hydrophobic interactions. The electro- of various elements including carbon (43.22%), oxygen (16.47%), so-
static force of attraction is a non-bonded interaction between two dium (18.54%), silicon (1.05%), sulphur (2.92%), chlorine (15.91%),
opposite charges of adsorbent and dye molecules. Hydrophilic and hy- potassium (0.66%), calcium (0.54%), and iron (0.68%). Thus,
drophobic interactions occur due to the presence of non-polar aromatic HR-SEM-EDX confirmed the adsorption of dye onto Gracilaria edulis
groups between the dye and CH3 group on the adsorbent surface (Giles biomass.
et al., 1960; Vo and Lee, 2017). XRD peaks reported that biosorbent exhibited both crystalline and
In summary, hydrogen bonds and π-π interactions were involved the amorphous nature (Figure 7). The crystallinity of biomass was evident
dye adsorption onto Gracilaria edulis however, more studies are required due to the presence of sharp peaks (Londo~ no-Restrepo et al., 2019).
to analyze the physicochemical properties of dyes (e.g., molecule size, n- Table 9 denotes the mineral composition of biomass. Average crystallite
octanol, and n-hexane-water partition coefficient) and the specific size calculated using the Debye-Scherrer equation was found to be
mechanism involved in their adsorption (Xiao and Pignatello, 2015). 104.19 nm. Vimala and Vedhi reported similar peaks for XRD analysis of
HR-SEM-EDX was used to study the morphological changes of bio- Gracilaria corticata (Vimala and Vedhi, 2019) which is closely related to
masses before and after the adsorption process. The analysis was per- Gracilaria edulis used in the current study.
formed under several magnifications viz., 3,000X, 10,000X, and BET surface area analysis revealed the total surface area of 0.271
30,000X. HR-SEM revealed that the surface of biomass before adsorption m2g1, total pore volume 0.01320 cm3g1, and mean pore diameter of
was found to be porous, vacant, and unoccupied (Figure 5 (a)). Whereas 283.69 nm biomass before and 0.132 m2g1, 0.00935 cm3g1, and
the biomass after adsorption showed the binding of dye on their surface 192.66 nm after adsorption respectively (Table 10). Results obtained
denotes a reduction in pore surface and pore volume significantly
contributed to the adsorption process. Low surface area is often a char-
acteristic feature of biological adsorbents and has been reported (Zhang
et al., 2013). Inyinbor et al., reported a total surface area of 0.0387 m2g1
and 1.8642 m2g1 for adsorption of Rhodamine B dye using agricultural
wastes (Inyinbor et al., 2015). Gracilaria edulis has a mean pore diameter
of 283.69 nm which corresponding to micropore size (>50 nm) would
have been due to the pretreatment of biomass (Hwang et al., 2018;
Kumar et al., 2019). Adsorbents with such macropore sizes are rarely
reported. BET isotherm and BJH pore size distribution were plotted
which elucidated the adsorption and desorption properties of biomass
with an increase in pressure (Figure 8). With an increase in the pressure,
adsorption of inert gas onto biomass increased significantly.
Response optimization for the current model was performed with the
target set as 99%. The optimized predicted response (decolorization
percentage) was found to be 92.55% at time 131.51 min; pH 7.48; dye
concentration 23.13%. The predicted optimized response was verified by
performing in the wet lab experimentally. The maximum response
(decolorization percentage) was found to be 92.65% (average of two
trials) which was comparatively higher than the predicted response and
thus proves the validity of the model.
9
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
Figure 5. HR-SEM images of Gracilaria edulis (a) before and (b) after adsorption under 3,000X magnification.
shaker at 150 rpm for 5 min. Thirteen trials were performed similarly to Desorption of dye was found to be highest at pH 2 with 23% possibly
determine the effect of pH on desorption. Adsorption and desorption due to the influence of Hþ ions at acidic pH competing with dye mole-
efficiencies were analyzed spectrophotometrically at 578.8 nm Figure 9 cules for the negatively charged binding sites on the adsorbent causing
shows the desorption of dye from adsorbed biomass at different pH and repulsion of dyes from adsorbent (Mahmood, 2014). The lowest
desorption efficiency was calculated using the equation (Eq. (6)). desorption was attained at pH 14 with 13.4% efficiency. This could be
due to the influence of OH attracting the dye towards the adsorbent due
Desorption (%) ¼ (Desorption absorbance – Adsorption absorbance) * 100 (6) to the electrostatic force of attraction (Mahmood, 2014).
Figure 6. Energy dispersive X-ray analysis showing various elements on dye adsorbed Gracilaria edulis.
10
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
and their effects were studied by them (Jegan et al., 2016). Their
maximum biosorption (decolorization) was found to be 181.0 mg/g at an
optimum particle size of 1.88 mm; biosorbent dosage of 5 g/L; pH 8; dye
concentration of 100 mg/L and contact time of 360 min. The current
study reported 92.65% efficiency with just 1 g/L of biomass concentra-
tion. The influence of basic pH was a predominant influential factor for
the adsorption of cationic onto algae. Biosorption of Basic Violet 14 onto
Gracilaria edulis was evaluated by Devi and Murugappan. Factors like pH,
biosorbent dosage, temperature, agitation speed, time, and particle size
were evaluated in their study. The adsorption of dye was very rapid and
has attained equilibrium at temperature 40 C and at time 90 min.
Maximum biosorption was 1250 mg/g at pH 10 was attained (Devi and
Murugappan, 2016). A Pseudo-second-order model could explain their
adsorption process. Devi et al. evaluated the adsorption of Reactive Blue
19 onto Gracilaria edulis. Parameters like pH, dye concentration, time,
adsorbent concentration, agitation, biosorbent size, and temperature
were optimized by them. Maximum biosorption was found to be 82.2
mg/g at pH (1.5), temperature (30 C), time (300 min), biosorbent size
(<75 mm), adsorbent concentration (1 g/L), and agitation speed (150
Figure 7. XRD result of Gracilaria edulis. rpm) (Devi et al., 2015). The present study proved maximum decolor-
ization efficiency of 92.65% could be attained which is comparable with
3.7. Discussion the decolorization efficiency attained by Devi and Murugappan (2016).
Sharifi and Shoja (2018) performed the biosorption of Methylene Blue
This section discusses the findings of the previously reported similar onto magnesium oxide nanoparticles coated spruce sawdust using
studies that use various adsorbents for the adsorption of textile dyes. The Box-Behnken design of response surface methodology reported
findings of the present work is compared with every previously reported maximum decolorization of 94% efficiency dye removal at pH 11, dye
study to project the efficiency of present study. There has been a handful concentration of 100 mg/L, and adsorbent dosage of 3.51 g/L was
of studies that tested the adsorption of live industrial effluent samples attained which is comparable with the current study of 92.65% decol-
containing a profusion of dyes, heavy metals, salts, acids, and other orization efficiency. Igwegbe et al. (2019) performed the adsorption of
contaminants expelled from industries. The majority of the studies pre- aqueous Methylene Blue onto Ho-CaWO4 nanoparticles using CCD and
viously done illuminate the insights of adsorption of synthetic dyes with artificial neural network optimization techniques. They reported a
known concentrations, the problem lies in the removal of wastewater maximum of 71.17% (103.09 mg/g) decolorization efficiency was
whose concentrations are not known such as described in the present attained after at pH 2.03, time 15.16 min, adsorbent dosage 1.91 g/L, and
study. The marine red macroalgae Gracilaria edulis was found to be a very dye concentration of 100.65 mg/L. The present study reported an effi-
potent biosorbent for the decolorization of textile dye effluent. Several ciency higher than them.
factors like pH, temperature, biomass concentration, dye concentration, Demirbas et al. (2008) studied the kinetic studies on adsorption of
time, and static-agitation were found to influence the biosorption of dyes. basic dye Astrazon Yellow 7GL onto the surface of apricot stone pre-
Biosorption of Crystal Violet (cationic dye) using marine red algae treated with sulphuric acid. Various operational parameters such as dye
Gracilaria edulis was studied by Jegan et al. (2016). Factors such as concentration, pH, sorbent dosage, time, and temperature were opti-
particle size, biosorbent dosage, pH, dye concentration, and contact time, mized in their study. Of the five parameters, three parameters namely
Table 10. Surface Characteristics of Gracilaria edulis using BET and BJH analysis.
Sample Total surface area (BET) (m2g1) Molar volume of gas (cm3 (STP) g1) Total pore volume (cm3g1) Mean pore diameter (nm)
Before adsorption 0.271 0.0631 0.01320 283.69
After adsorption 0.132 0.0303 0.00935 192.66
11
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
Figure 8. BET adsorption-desorption isotherm of inert N2 onto Gracilaria edulis and BJH pore size distribution.
Desorption of dye
30
Scale:
x axis: 1 interval =
25 5%
23
y axis: 1 interval =
21 20.7 2 (no units)
20 19.7 19.6
20
18
Desorption (%)
16 15.5
15 14 13.5 13.5 13.4
Desorption (%)
10
0
2 3 4 5 6 7 8 9 10 11 12 13 14
pH
pH, biosorbent dosage, and temperature were found to influence the that adsorption of Methylene Blue occurred faster than safranin in binary
adsorption process. Maximum adsorption was attained at pH 10, sorbent solutions nevertheless the time needed for acquiring equilibrium, fixed
dosage 6 g/L, and time 35 min respectively. The data were fitted onto bed parameters, and adsorptive capacity varied for the two compounds.
Langmuir and Freundlich isotherms in their study. The maximum Sharma and Das (2012) studied the adsorption efficiency of graphene
adsorption efficiency was found to be 221.23 mg/g at 50 C. Values of oxide nanosheets. Methyl Green, a cationic dye was used in this study and
entropy and enthalpy were found to be 31.93 J/mol K and 49.87 kJ/mol is reported to be one of the most toxic dye. Adsorption of Methyl Green
indicated that the model was spontaneous and endothermic. Rozada et al. onto graphene oxide nanosheet was mainly due to the presence of
(2003) studied the adsorption of dyes onto activated carbon produced functional groups such as epoxy, carboxyl, and hydroxyl functional
from pyrolysis of sewage sludge and chemical activation methods. Their groups imparting negatively charged functional groups onto its surface.
experiment was performed using liquid-phase adsorption tests onto Adsorption kinetics, biomass concentration, pH (4–9), and temperature
activated carbon. Colored aqueous dye solutions such as Methylene Blue (25 C) and their effects were studied. The adsorption mechanism and
and Safranin were used in their study. Their experiment was performed interactions were studied using various kinetic models Boyd model,
using batch and fixed-batch methods (Rozada et al., 2003). They reported Intraparticle diffusion, pseudo-first-order model, pseudo-second-order
12
R. Venkataraghavan et al. Heliyon 6 (2020) e05219
model. The results were reported that maximum adsorption was attained study to find out the important significant factors influencing the bio-
at 60 min using a pseudo-second-order kinetic model. Their data were sorption of dye effluent onto biomass. Out of six factors, three factors
well fitted onto the Langmuir isotherm model. Enthalpy, entropy and namely time, pH, and dye concentrations were found to exert a signifi-
Gibbs free energy of the experiment were also evaluated and proved that cant effect on the process. The three factors were further optimized using
the reaction was spontaneous. Their experiment was confirmed using Box-Behnken of Response Surface Methodology to get the optimized
diffuse reflectance infrared Fourier transform spectroscopy. Oyekanmi values of each factor for maximum decolorization. The maximum
et al. (2019) reported maximum decolorization efficiency of 89.82% and decolorization using RSM-BB design was attained at time 130.9 min, pH
69.96% COD reduction through adsorption of Rhodamine B dye onto 7.0, and dye concentration 16.56% respectively. The predicted (92.56%)
acid pre-treated banana peels using CCD of RSM. Maximum decoloriza- and the experimental (92.65%) values were found to be in a good
tion and COD reduction was attained at pH 2, adsorbent dosage of 0.2 g/L agreement under the optimized conditions. The experiment was
and contact time of 60 min and is comparable with the efficiency of the confirmed using FTIR, HR-SEM-EDX, and BET techniques. The desorp-
present study with 92.65%. The experiment was best explained by tion of adsorbed dye promotes the reusability of biomass in the future.
Langmuir adsorption isotherm model. Maximum desorption of 23% from the adsorbed biomass was obtained at
Sadaf and Bhatti performed the adsorption of Indosol Yellow BG from pH 2. Thus, by using the statistical optimization designs, we can able to
aqueous solution onto agricultural biomass, peanut husk. The Box- save time, cost, effort, and labor spent on the conventional method of dye
Behnken design was used for their study. They reported a maximum of decolorization. In the future, Gracilaria edulis can be immobilized using
58.01 mg of dye adsorbed onto 1 g of acetic acid-treated biomass at an calcium chloride and sodium alginate to promote reusability. A batch
initial concentration of 200 mg/L at pH 2, and biomass dosage of 0.17 g. reactor can be designed to enhance the process from lab-scale to pilot-
They also recovered 44.5% dye from the adsorbed biomass using 1 M scale.
NaOH which is nearly double the efficiency of desorption compared to
the present study (Sadaf and Bhatti, 2015). Postai and Rodrigues (2018) Declarations
studied the adsorption of cationic Methylene Blue and Rhodamine B onto
low-cost treated and untreated fruit waste Eugenia umbelliflora in a batch Author contribution statement
system. The adsorbent was characterized by them for the point of zero
charge, the presence of functional groups using FTIR, and thermogravi- Venkataraghavan R: Conceived and designed the experiments;
metric properties. The adsorption process was studied using the Sips Analyzed and interpreted the data; Wrote the paper.
equation which best suited the model. Maximum adsorption for the un- Thiruchelvi R: Conceived and designed the experiments; Contributed
treated Eugenia umbelliflora was found to be 157.2 mg/g for Methylene reagents, materials, analysis tools or data.
Blue and 161.1 mg/g for Rhodamine B. Maximum adsorption efficiency Sharmila D:Performed the experiments.
for the treated Eugenia umbelliflora was found to be 111.6 mg/g for
Methylene Blue and 106.4 mg/g for Rhodamine B. The adsorption of Funding statement
cationic dyes onto adsorbent followed pseudo-first-order kinetics and is
comparable with the current finding with maximum decolorization of This research did not receive any specific grant from funding agencies
92.65%. Their experimental model was found to be spontaneous and in the public, commercial, or not-for-profit sectors.
exothermic. The process parameters were optimized using 3-level
Box-Behnken design, and the initial dye concentration was found to be Competing interest statement
the best influential factor for adsorption. The results were promising and
Eugenia umbelliflora could be used as potential adsorbent for the The authors declare no conflict of interest.
large-scale dye removal process. Mahmood (2014) reported that a
maximum of 13.4% was obtained at pH 12.6 for desorption of Direct Additional information
Yellow 28 dye. The results of desorption reported by Mahmood (2014) is
comparable with the current finding of 23% desorption efficiency. Jain No additional information is available for this paper.
et al. (2010) reported the desorption of Naphthol Yellow S from adsor-
bent using various concentrations of sodium hydroxide. Dilute concen- Acknowledgements
trations of sodium hydroxide through a fixed bed along the adsorbent
column had a significant impact on regeneration. Berez et al. (2014) The authors sincerely thank Vels, Institute of Science, Technology and
reported that a maximum of 46 and 68% of Feron Blue 291 dye adsorbed Advanced Studies and Dr. M. Ganesan, Senior Scientist, CSIR-CSMCRI for
onto bentonite could be desorbed using kinetic studies which is much their sincere support towards the successful completion of the research
higher than the current finding reported in this work with 23% desorp- work. The authors sincerely thank the reviewers for suggesting valuable
tion efficiency. comments towards the improvement of our article to attain publishable
Thus, this section concludes by comparing the results and efficiency status. The authors also thank Sophisticated instruments facility, Vellore
of the present with the previously reported different types of adsorbent institute of technology, Government of India and Sophisticated analytical
materials and dyes. From the discussion, the outcomes of the present instruments facility, Indian Institute of Technology, Madras and
study are very efficient when compared with the adsorption potential of Department of Science and Technology and Central Instrumentation
synthetic dyes onto several types of biomasses and further studies are to Facility, Vels Institute of Science, Technology and Advanced Studies for
be carried out to develop small-scale commercialization. performing characterization studies.
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