Accepted Manuscript

Title: Adsorptive potential of agricultural wastes for removal

of dyes from aqueous solutions

Author: Hemant Singh Garima Chauhan Arinjay K. Jain S.K.

Sharma

PII: S2213-3437(16)30422-5
DOI: http://dx.doi.org/doi:10.1016/j.jece.2016.11.030
Reference: JECE 1343

To appear in:

Received date: 29-8-2016

Revised date: 20-11-2016
Accepted date: 22-11-2016

Please cite this article as: Hemant Singh, Garima Chauhan, Arinjay K.Jain,
S.K.Sharma, Adsorptive potential of agricultural wastes for removal of dyes
from aqueous solutions, Journal of Environmental Chemical Engineering
http://dx.doi.org/10.1016/j.jece.2016.11.030

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 ADSORPTIVE POTENTIAL OF AGRICULTURAL WASTES FOR
REMOVAL OF DYES FROM AQUEOUS SOLUTIONS
Hemant Singh, Garima Chauhan*, Arinjay K. Jain*, S. K. Sharma
University School of Chemical Technology, Guru Gobind Singh Indraprastha University, New Delhi-110078
*Corresponding author: [email protected]
[email protected]

Graphical abstract

Highlights :

1. Novel green adsorbents were explored for removal of dyes from waste water.

2. Proposed an economic incentive to industrial practice for waste management.

3. Possibility of mass transfer resistance and kinetic aspects was investigated.

4. More than 90% dye removal was obtained for all investigated dye-adsorbent

systems.

5. Isotherms and kinetics were examined to look into adsorbate-adsorbent

interaction.

1
Abstract

Present work aims to investigate the adsorptive characteristics of agricultural wastes

(Citrus Limetta Peel and Zea Mays Cob) for effective removal of dyes from aqueous

solutions. Batch adsorption experiments were carried out in order to analyse

sorption behaviour of dye-adsorbent systems at different adsorbent dosage and

initial dye concentration. Possibility of mass transfer resistance was investigated to

improve the diffusion rate, whereas kinetic aspects were examined to achieve

thermodynamic equilibrium for the proposed adsorption process. Solution pH was

observed to significantly affect the adsorption efficiency by regulating degree of

ionization of the adsorbate’s functional groups. More than 90% removal of dyes was

attained for all dye-adsorbent systems under optimum reaction conditions.

Characterization studies were performed to examine the changes in morphology and

functional groups of the adsorbents before and after adsorption process. Kinetic

study suggested the pseudo-second kinetic model with normalized standard

deviation Δqt (%) < 5% and regression coefficient > 0.999 as being able to better

describe kinetic data than pseudo first order and elovich kinetic models. Adsorbate-

adsorbent interaction was investigated by looking into the applicability of Langmuir,

Freundlich and Dubinin-Radushkevich isotherms for the proposed adsorption

process. Maximum adsorption capacity Q° was observed to be highest for malachite

green dye (8.733 mg/g and 16.72 mg/g) using CLP and ZMC respectively. Findings

obtained from thermodynamic studies indicated endothermic and spontaneous

nature of the proposed process. This work offers an economic incentive to the

industrial practice for waste management and eofriendly approach for removal of

toxic dyes from textile waste water.

2
Keywords

Green adsorbents, equilibrium studies, kinetics, thermodynamics, characterization

1. Introduction

Unprecedented growth of industries, in spite of playing an important role in mankind

welfare, has left a significant negative impression on the ecosystem. Many industries

such as textile, paint, leather etc. use dyes for colouring their products and large

3
volume of effluents containing several dye organics is heedlessly discharged into the

surface water bodies without any prior treatment. Presence of dyes, even at small

amounts (<1 mg/L) in the industrial effluent, is a sincere matter of concern for both

toxicological and esthetical reasons [1]. Dyes can affect the biological metabolism

process by interfering the transmission of sunlight through water [2]. Also dyes have

tendency to sequester metal ions and thus may engender toxicity to aquatic life.

Mutagenic and carcinogenic nature of dyes may impart hazardous health effects

such as dysfunction of kidneys, central nervous system and reproductive system.

Several biological, physicochemical and electrochemical treatment methods have

been reported in literature [3-6] however high process cost, secondary pollution

possibilities, use of toxic reagents and long process time confine the use of these

conventional methods at industrial scale. Therefore, a strong need is felt to develop

an effective eco-friendly process for the removal of dyes from industrial wastewater.

Adsorption process has been found to be superior among the existing processes for

water treatment due to high efficiency, flexibility, ease of operation, insensitivity

towards toxic pollutants and economic feasibility [1,7,8]. Activated carbon (AC) has

shown considerable good dye removal efficiency [9,10] though practical application

of AC is limited due to problems associated with its regeneration or disposal, sludge

production and economic feasibility [11,12]. Recently, agricultural and industrial

wastes [13-17] have dictated the researcher’s interest owing to their wide availability,

low cost, less commercial value and biodegradable properties. Babalola et al. [18]

investigated the adsorption efficiency of a plant waste Cedrela odorata Seed Chaff

(COSC) for the adsorption of industrial dyes from aqueous solutions. Microstructures

of COSC indicated presence of various organic moieties which are responsible for

efficient adsorption of toxic dyes. Unuabonah et al. [19] performed continuous

4
adsorption studies in a fixed bed reactor using a novel hybrid adsorbent (a

combination of Carica papaya seeds and Kaolinite clay) and reported breakthrough

adsorption capacity of 35.46 mg/g for the adsorption of methylene blue dye.

Regeneration possibilities, significant adsorption capacity and economical feasibility

make this proposed hybrid adsorbent as a promising alternative. Tree waste

Pentaclethramacrophylla tree bark and Malacanthaalnifolia tree bark were employed

as low-cost adsorbent for the removal of toxic dyes and heavy metals (Cd 2+, Pb2+)

from aqueous solutions [20]. Adsorption efficiency of the adsorbents was optimized

by varying various process parameters such as pH, biomass dose, initial solute ion

concentration, agitation time and temperature [20]. Biosorption potential of

abundantly available waste biomass Zea mays seed chaff was investigated for the

removal of heavy metals (Cr3+,Cd2+ and Pb2+) from aqueous solutions. Authors

suggested endothermic nature of the biosorption of these metals with large positive

entropy values [21]. Adsorption potential of lignocellulosic material (native and

modified form) was investigated for the effective removal of Direct Yellow 50 dye

from aqueous solution under batch and continuous mode [22]. Modified biosorbents

demonstrated the enhanced biosorption capacity than native and immobilized forms.

Polyethylenimine treated peanut-husk biomass was also illustrated as an efficient

biosorbent for the removal of Indosol Black NF and Indosol Orange RSN dyes from

aqueous solutions and desorption study were conducted to look into the possibility of

regeneration of bioadsorbent [23]. Maximum dye removal (58.01 mg/g) was

achieved at 200 mg/L initial dye concentration, pH 2.0, and 0.17 g peanut husk

adsorbent dose by optimizing the process parameters using response surface

methodology [24].

5
Present study explores the adsorption potential of Citrus Limetta Peel (CLP) and Zea

Mays Cobs (ZMC) for the removal of three different textile dyes (Malachite Green

(MG), Methylene Blue (MB), Congo Red (CR)) from synthetic samples. Citrus

Limetta (Sweet Lemon) and Zea Mays (Corn) are considered important fruit and

cereal crops respectively across the globe and are produced in more than 100

countries. Nearly 115 million ton production of citrus across the globe was reported

in year 2012 which is predominantly contributed by China, Brazil, USA and India

[25]. Zea Mays is currently the second most abundant crop globally [26,27] and is

predicted to surpass both wheat and rice to become the number one grain at global

scale by 2020 [28]. Nearly 968 million tons of corn production is reported globally in

year 2015-16 in which USA contributes to more than 35% of total production [29].

Consequently, large amount of sweet lemon peels and corn-cobs are produced

every year from these crops. These agricultural by-products are structurally

composed of cellulose, hemicellulose, lignin and protein content, therefore their

direct disposal in ecosystem may increase the biological oxygen demand of water

and putrefaction of biomass [30].

To the best of our knowledge, removal of MB, MG and CR textile dyes has not been

examined yet using CLP and ZMC as green adsorbents. The focus of the study was

to investigate mass transfer limitations, equilibrium and kinetic aspects in order to

optimize the dye adsorption efficiency of the proposed novel low-cost adsorbents.

Various characterization techniques were employed to investigate the changes in

physico-chemical properties of fresh and dye-loaded adsorbents.

2. Material And Methods

2.1. Synthetic Dyes

6
Methylene blue (MB), also known as tetramethylthionine chloride is a cationic

thiazine dye which consists of dark green crystals or crystalline powder and has a

bronze-like luster. It is one of the most commonly used dyes in textile industry for

dying cotton, wool and silk. Exposure to MB has been reported to cause increased

heart rate, cyanosis, nausea, jaundice, quadriplegia, Heinz body formation and

tissue necrosis in humans. Iris epithelium, corneal and conjunctival injury [31],

neurotoxic effects on central nervous system [32], serotonin toxicity [33] and

teratogenic effects [34] have also been reported widely due to acute exposure to MB

dye. Table 1 describes the main characteristics of each dye employed in present

study.

Malachite Green (MG), a cationic N-methylated diaminotriphenylmethane dye, exists

as a mixture of chromatic malachite green cation and its carbinol base in solution

[35]. It is extensively used in dyeing of textile material and in distilleries. Applicability

of MG as a therapeutic agent in aquaculture has also been reported widely.

However, excessive exposure of MG may cause teratogenicity, respiratory toxicity

carcinogenesis, mutagenesis and chromosomal fractures [36,37].

Congo Red (1- Naphthalenesulfonic acid, 3, 3'-(4, 4' biphenylene bis (azo) bis 4-

amino) di sodium salt) is known to metabolize to a human carcinogen benzedene.

Acute exposure of this dye may cause an allergic reaction and anaphylactic shock.

Therefore, the treatment of effluent containing toxic dyes is of sincere concern these

days.

2.2. Preparation And Characterization of Low-Cost Adsorbents

CLP and ZMC samples were collected from local vendor, New Delhi (INDIA) and

washed thoroughly using distilled water in order to remove the impurities present on

the surface. The samples were dried in presence of sunlight for 5 - 7 days.

7
Completely dried material was grinded to powder and then sieved using 40 mesh

screen in order to obtain the desired particle size. The powdered sample was finally

dried in a hot air oven at 100°C for 2 h and was stored in an airtight vessel. It was

used directly for batch adsorption experiments without any further treatment. Figure

1 demonstrates raw material and the grinded form (150 µm particle size) of the

prepared adsorbents.

Figure 1 : Preparation of Low-cost adsorbents (A) CLP (B) ZMC

Proximate analysis was performed in order to estimate the moisture, ash, volatile

matter and carbon content in fresh samples of CLP and ZMC adsorbents. Fourier

Transform Infrared (FTIR) spectroscopic analysis was performed for the

determination of functional groups on the adsorbent surface. Samples for FTIR

analysis were prepared using KBr powder as illustrated in literature [38]. Pellets were

prepared by mixing 0.5 g of adsorbent in sufficient amount of potassium bromide

(KBr). FTIR spectra of the raw material and residue obtained after adsorption

experiments were recorded using FTIR spectrophotometer (Nicolet IS50) within the

range 500 - 4000 cm-1. Surface morphology of raw and dye loaded adsorbents was

investigated with the aid of Scanning Electron Microscopic Analysis (SEM EVO 50)

operated at 20 kV accelerated voltage and magnification of 3KX and of 20KX. Gold

coating was provided on non-conducting adsorbents with the aid of vacuum

evaporation to get uniform thickness of specimen during analysis [39].

2.3. Adsorption Experiments:

100 mg/L stock solutions were prepared by dissolving accurately weighed amounts

of MB, CR and MG dyes in 1 L of distilled water. Working solutions were prepared by

diluting the stock solutions into various working concentrations ranging from 5 mg/L

8
to 25 mg/L. Amount of adsorbent was varied for a wide range (0.25 g – 2.5 g) in

order to determine the optimum adsorbent dose. pH of the aqueous solutions was

adjusted by adding 0.1 M HCl or NaOH solutions. Adsorption experiments were

performed at room temperature and constant stirring speed of 150 rpm for a certain

agitation time in order to achieve equilibrium. Once equilibrium is attained, the

supernatant liquids were filtered and residual dye concentration was determined

using UV/vis spectrophotometer (Hitachi UV-2900). Influence of reaction pH (3.0 -

12.0), initial dye concentration (5 - 25 mg/L), reaction time (10 - 60 min) and reaction

temperature (303 - 333 K) were investigated. The amount of dye adsorbed was

calculated using following expression given in equation (1):

𝐶0 −𝐶𝑒
𝑞𝑒 = ( )∗𝑉 …………….(1)
𝑊

where, qe = Amount of dye adsorbed per unit mass of adsorbent (mg/g) at

equilibrium, C0 = initial dye concentration (mg/L), Ce = dye concentration in the

solution at equilibrium (mg/L), V = Volume of the synthetic solution (L), w = weight of

the adsorbent (g).

2.4. Adsorption Kinetic Studies

Kinetics of the adsorption process was evaluated in the present study to determine

the rate of adsorption. Pseudo first order and second order models have been used

widely in literature to investigate the kinetics associated with the adsorption of

metals and dyes from aqueous solutions [13,17,40]. Applicability of these kinetic

models was investigated in the present study to estimate the rate of adsorption of

MB, MG and CR dyes on CLP and ZMC adsorbents. Elovich equation was also

chosen to model the kinetic data obtained from this study.

9
Lagergren pseudo-first order kinetic model is employed to investigate adsorption of

liquid-solid system on the basis of adsorbent capacity [41] in which one adsorbate

species reacts with one active site on surface. The linearized form of the pseudo first

order kinetic model is given in equation (2) [41] :

ln(𝑞𝑒 − 𝑞𝑡 ) = ln(𝑞𝑒 ) − 𝑘1 𝑡 …………….(2)

where qe is the amount of adsorbate adsorbed at equilibrium (mg/g), qt is the amount

of solute adsorbed per unit weight of adsorbent at time t (mg/g), k 1 is the rate

constant of pseudo first order adsorption (min-1). Plot of ln (qe-qt) vs time was drawn

for all the three employed dyes and values of k1 and qe,cal were calculated from the

slope and intercept respectively.

The linearized form of pseudo-second-order equation is given here in equation (3)

[42] :

𝑡 1 𝑡
= 2 + ………………(3)
𝑞𝑡 𝑘2 𝑞𝑒 𝑞𝑒

Linear plot of t/qt versus t was drawn and values of qe and k2 were calculated from

the slope and intercept respectively. Initial sorption rate (h = k2qe2) at t = 0 was

estimated using the value of pseudo second order rate constant k2.

Linear form of the elovich kinetic model is given in equation (4) [43] :
1 1
𝑞𝑡 = ln(𝛼𝛽) + 𝛽 ln(𝑡) ……………… (4)
𝛽

where α is the initial desorption rate (mg/(g min)) and β is the desorption constant

(g/mg). Available adsorption sites (1/β) was calculated from the slope of linear plot of

qt versus ln(t). Intercept (1/β)ln(αβ) indicates the adsorption quantity when ln(t) = 0

2.5. Error Analysis

10
The applicability of the employed kinetic models was analysed on the basis of linear

regression coefficient (R2), normalized standard deviation (Δqt (%)) and average

relative error (ARE). Δqt(%) and (%)ARE were calculated using equation (5) and

equation (6) [44] respectively.

2
(𝑞𝑒𝑥𝑝 −𝑞𝑐𝑎𝑙 )
100√∑𝑁
𝑖=1(
⁄𝑞
𝑒𝑥𝑝
)
∆𝑞𝑡 (%) = ………………..(5)
𝑁−1

100 𝑞𝑒𝑥𝑝 −𝑞𝑐𝑎𝑙

𝐴𝑅𝐸(%) = ∗ ∑𝑁
𝑖=1 | | ………………..(6)
𝑁 𝑞𝑒𝑥𝑝
𝑖

where N is the number of data points, qexp and qcal (mg/g) are the experimental and

calculated adsorption capacity values.

2.6. Adsorption Equilibrium Studies

In order to understand the nature of interaction between adsorbate and adsorbent,

different isotherm models namely Langmuir, Freundlich and Dubinin–Radushkevich

(D–R) were employed in present study.

2.6.1. Langmuir Isotherm

The Langmuir isotherm is based upon an assumption of monolayer adsorption onto

adsorbent surface with a finite number of adsorption sites of uniform energies [45].

Linearized form of langmuir equation is given as mentioned in equation (7) [46] :

𝐶𝑒 1 𝐶𝑒
= + ...…………..(7)
𝑞𝑒 𝑄0 𝑏 𝑄0

where, Ce is the equilibrium concentration of adsorbate (mg/L), qe is the amount of

adsorbate adsorbed per unit mass of adsorbent (mg/g), Q 0 is the monolayer

adsorption capacity (mg/g) and b is the Langmuir constant related to the free energy

of adsorption (L/mg). Slope and intercept of the linear plot of C e/qe versus Ce give

values of b and Q0 respectively. Separation factor (RL) is also an essential

11
characteristic of langmuir isotherm to determine the feasibility of adsorption process.

It is represented as shown in equation (8) :

1
𝑅𝐿 = ………………(8)
1+𝑏𝐶0

where Co and b denote the dye concentration and langmuir constant respectively. If

RL = 0, adsorption is irreversible; 0 < RL < 1, adsorption is favourable and RL > 1,

adsorption is unfavourable.

2.6.2. Freundlich Isotherm

The Freundlich isotherm assumes that heterogeneity of the adsorbent surface and

the capacity of adsorption are related to the dye concentration at equilibrium. The

freundlich equation [47] is expressed in linear form as shown in equation (9) :

1
𝑙𝑛𝑞𝑒 = 𝑙𝑛𝐾𝑓 + 𝑙𝑛𝐶𝑒 ………………..(9)
𝑛

where Kf is the freundlich constant related to bonding energy and n represents

surface heterogeneity factor that indicates the adsorption intensity. The values of K f

and n were calculated from the intercept and slope of linear plot ln(q e) vs ln(Ce). The

value of ‘n’ is considered a measure to estimate the favourability of the sorption

process. Values of n > 1 represent favourable adsorption condition [48,49].

2.6.3. Dubinin-Rahushkevich (D-R) isotherm

The equilibrium data were also applied to the Dubinin-Radushkevich (D–R) isotherm

model [50] in order to determine the type of sorption (physical or chemical) process.

The linearized form of D–R equation is given in equation (10) :

ln(𝑞𝑒 ) = ln(𝑞𝑚 ) − 𝛽𝜀 2 ………………………(10)

12
where qe (mg/g) is the amount of dye adsorbed onto per unit dosage of adsorbent

(CLP or ZMC), qm is the theoretical monolayer sorption capacity (mg/g), β (mol 2/J2)

is related to the average energy of sorption per mole of the adsorbate as it is

transferred to the surface of the solid from infinite, ε is Polanyi potential which is

calculated using equation (11) [51] :

1
𝜀 2 = 𝑅𝑇𝑙𝑛 (1 + 𝐶 ) ………………………(11)
𝑒

where, R is universal gas constant (8.314 J/mol.K), T is the absolute temperature

(K). Slope and intercept of linear plot of ln(qe) vs ε2 give the value of β and qm

respectively. The mean adsorption energy (E) was calculated from constant β using

the relation given in equation (12) :

1
𝐸= ………...……(12)
√2𝛽

If the magnitude of E is between 8 and 16 kJ/mol, then adsorption process proceeds

via chemisorption, while for values of E < 8 kJ/mol, the adsorption process is

considered to be of physical nature [30,45].

2.7. Thermodynamics Studies

Feasibility of experimental data obtained from the adsorption studies were analysed

through thermodynamic investigation. Thermodynamic parameters such as standard

free energy change (ΔG°, kJ/mol), enthalpy change (ΔH°, kJ/mol) and entropy

change (ΔS°, J/mol/K) were determined using Van't Hoff equation as expressed in

equation (13) and equation (14) :

∆𝑆 0 ∆𝐻 0
ln(𝐾𝑑 ) = − ………………………(13)
𝑅 𝑅𝑇

∆𝐺 0 = ∆𝐻 0 − 𝑇∆𝑆 0 ………………………(14)

13
Kd refers to the standard thermodynamic equilibrium defined by C ad/Ce, where Cad

(mg/L on solid adsorbent) and Ce (mg/L in the solution). R is the universal gas

constant (8.314 J/mol.K), and T is the absolute temperature (K).

3. Results and Discussions

3.1. Spectrophotometric Calibration

Dye Concentration in each aqueous solution was determined with the aid of Hitachi

U-2900 UV spectrophotometer fitted with 3 mm quartz cells. Standard solutions of

varying concentration of individual dye (MB, MG, CR) were prepared by dissolving

suitable amount of the dye in 100 mL of water. The absorbance was measured at

wavelength range from 800 nm to 200 nm against the reagent blank. Maximum

absorbance for MB, MG and CR dye were detected at 666 nm, 615 nm and 499 nm

respectively. Calibration plot was prepared for each dye by plotting concentration of

dye (mg/L) versus absorbance. The unknown concentration of dye in the residual

supernatant was calculated using equations (15) – (17) obtained from calibration

curve.

Methylene Blue : Y = 0.143x + 0.0558 (R2 = 0.97)…...……………………...(15)

Malachite Green : Y = 0.0236x - 0.0029 (R2 = 0.99)...………………………...(16)

Congo Red : Y = 0.1639x - 0.0218 (R2 = 0.99)..…………………………(17)

where Y is the absorbance of spectrophotometer and X is the amount of dye (mg/L).

3.2. Characterization of Adsorbents

3.2.1. Proximate Analysis

Proximate analysis was performed in order to estimate the moisture, ash, volatile

matter and carbon content in fresh samples of CLP and ZMC adsorbents. 2 g of raw

14
material was weighed and kept in hot air oven at 105°C (90 min.), 650°C (30 min.),

910°C (7 min.) for the estimation of moisture, ash and volatile matter content

respectively using following equations (18) – (20).

𝑆−𝐷
Moisture Content 𝑀 = 100 ∗ ( 𝑆−𝐹 ) ………………(18)

𝐷−𝐹
Ash Content 𝐴 = 100 ∗ ( 𝑆−𝐹 ) ………………(19)

(S−D)−(M∗(S−F))
Volatile Matter 𝑉 = 100 ∗ (S−F)∗(100−M)
………………(20)

Here, F = Mass of empty crucible; S = mass of crucible + sample; D = mass of

crucible plus sample after drying. Percentage of carbon content was determined by

summing up the percentage content of the above described parameters and then

subtracting it from 100 as shown in equation (21) :

% Carbon Content = 100 – (% M + % V + % A) …………..…..(21)

Table 2 lists the moisture, ash, volatile matter and carbon content obtained from

proximate analysis for both the low-cost adsorbents. It can be observed from Table 2

that the raw materials are rich in moisture and volatile matter content, whereas ash

content was found to be non-significant in the adsorbents. Carbon content was more

than 10% in both the samples which substantiate the acceptability of these raw

materials as green adsorbents for dye removal from waste water.

Surface Chemistry

FTIR spectra of raw material and dye loaded adsorbents are shown here in Figure

2(A) and Figure 2(B) for CLP and ZMC respectively. FTIR spectra clearly revealed

reduction, disappearance or broadening of the peaks after adsorption of MB, MG or

CR dyes on the CLP and ZMC adsorbents. Figure 2(A) reveals the characteristic

15
broad peak at 3424 cm-1 due to O-H stretching vibration of hydroxyl functional

groups. The absorption band at 2925 cm−1 corresponds to the symmetric C–H

stretching of alkane group in cellulose and hemicellulose [30]. Other major peaks at

bandwidths of 1752 cm-1, 1611 cm-1, 1521 cm-1, 1383 cm-1 attributed to C=C

stretching of alkynes, vibration of C=O stretching of lactones, ketones, and

carboxylic anhydrides, C=C of aromatic ring and C–H stretching in alkanes or alkyl

group respectively. The C-O stretching vibration in cellulose, hemicellulose and lignin

can be corroborated for the absorption peaks at 1233 cm −1 and 1100 cm−1 [52,53].

Dye loaded adsorbents exhibited disappearance of peaks at band position 1521cm-1,

1438 cm-1 and 1233 cm-1 whereas appearance of some new peaks suggested the

possibility of adsorbate-adsorbent interactions [54]. The peak representing O–H

stretching vibration gets shifted from 3424 cm−1 to 3484 cm−1 for MB while CR and

MG loaded adsorbent did not show any shift in the bandwidth.

Figure 2(A) : FTIR spectra of raw and dye loaded CLP adsorbent.

Figure 2(B) demonstrates the FTIR spectra of fresh and dye loaded ZMC. A broad

band around 3447 cm-1 indicates the stretching vibration of O–H bond in hydroxyl

groups, though the peaks were shifted from 3447 cm -1 to 3416, 3425 and 3429 cm-1

for CR, MG and MB respectively. The peak at 1654 cm -1 in raw material corresponds

to bending vibration of O–H groups and was observed to shift at 1634 cm -1 for MG

and MB dye loaded ZMC. It may correspond to the involvement of hydrogen of O-H

group in the formation of surface complex with intramolecular hydrogen bonding

which facilitate the sorption of dye molecule onto the adsorbent surface [55]. The

peaks observed at 2923 and 1383 cm -1 were assigned to stretching and bending

vibration of C–H bond in methyl groups respectively whereas peak located at 1735

16
cm-1 attributed to carbonyl group stretching [56]. The strong C–O band at 1053 cm-1

corroborates the lignin structure of the ZMC [57]. The peak at 1246 cm-1 may

represent the stretching vibration of C–O in phenols. The slight changes in vibration

frequencies as a result of the adsorption of dyes onto ZMC and CLP corresponds to

complexation, chelation, precipitation and ion-exchange reactions which probably

took place in the functional moieties on the adsorbent surface [20].

Figure 2(B) : FTIR spectra of raw and dye loaded Zea Mays Cobs Adsorbent.

3.2.2. Surface Morphology

The morphological analysis of the adsorbent surface was conducted through SEM

analysis. Figure 3(A) and Figure 3(B) demonstrate the textural and porous features

of CLP and ZMC adsorbents respectively. Well-developed cavernous porous

structures were clearly visible in micrographs which may assist in accommodating

large amount of dye molecules from synthetic aqueous solutions to the adsorbent

surface. After the adsorption of MB, MG and CR dyes on CLP and ZMC surface,

significant change is observed in surface texture of the dye loaded adsorbent.

Surface was observed to be partially covered by dye compounds. SEM images of

dye loaded adsorbents are shown in Figure S-1 of the supporting information.

Agglomeration, cluster formation and a thin layer of dye on adsorbents were clearly

seen in the SEM images which articulate efficient adsorption of dyes.

Figure 3 : SEM Images of (A) Fresh CLP (B) Fresh ZMC Adsorbents

3.3. Effect of Reaction pH on Dye Adsorption

Solution pH influences the surface properties of adsorbents by regulating degree of

ionization of the dye’s functional groups and thus plays an important role in the dye

17
removal process from wastewater [54]. The effect of pH on the adsorption of dyes

using CLP and ZMC was investigated by varying the solution pH over a range of 2.0

to 12.0 and results are shown in Figure 4(A) & Figure 4(B) respectively. It can be

clearly depicted from Figure 4 that MG and MB dye removal efficiency increased with

an increase in solution pH whereas decrease in CR adsorption efficiency was

observed at alkaline pH. Similar results for the adsorption of MB, MG and CR were

reported in literature [30,58].

Figure 4 (A) : Effect of solution pH on adsorption capacity (mg/g) (red lines)

and (%) adsorption efficiency of CLP adsorbent (black lines) (Adsorbent dose :

MB (1.5 g), MG (0.5 g), CR (0.5 g); Initial dye conc. = 10 mg/L; agitation time = 30

min.; settling time = 1 h; stirring speed = 150 rpm)

Figure 4 (B) : Effect of solution pH on adsorption capacity (mg/g) (red lines)

and (%) adsorption efficiency of ZMC adsorbent (black lines) (Adsorbent dose :

(MB (1.5 g), MG (0.25 g), CR (1.25 g); Initial dye conc. = 10 mg/L ; agitation time =

30 min.; settling time = 1 h; stirring speed = 150 rpm)

The pH dependent adsorption performance of these dyes can be explained on the

basis of pKa value of adsorbate and the pHzpc of the adsorbent. pKa values of MG

and MB were reported as 6.9 and 5.8 respectively [30,59] which can be related with

the possibility of existence of these dyes in cationic form at pH > pKa and in anionic

form at pH < pKa. Number of hydroxyl group ions increases at the alkaline solution

pH which results into an increase in number of negatively charged sites and

consequently, enhances the attraction between positively charged dye and

adsorbent surface. The adsorbent surface becomes deprotonated due to availability

of large number of hydroxyl ions (pH > pHzpc), thus adsorbate cations move towards

18
negatively charged sites on CLP/ZMC surface through electrostatic attraction.

Similar results were reported in literature for the adsorption of MB/ MG dyes.

Kushwaha et al. [56] suggested that at pH 7.0, surface of Dacus Carota adsorbent

was negatively charged to its maximum extent, therefore further increase in pH did

not increase surface charge intensity as well as adsorption capability. Amode et al.

[60] illustrated a steady decrease in the amount of MB being adsorbed with increase

in pH from 4.0 – 12.0. Maximum adsorption of dye between pH values of 6.0 – 10.0

can be attributed to electrostatic attraction between the negative charges of the

adsorbent surface and the positive charge of the MB cation, since the amount of dye

being removed was high (>140 mg/g) at ambient pH (MB = 4.6)). On the other hand,

Babalola et al. [20] reported that the removal of MB onto plant waste biosorbents

was highest at pH 12.0 due to the low proton densities on the surfaces of these

biosorbents at alkaline pH.

In contrast to MB and MG dye, CR is an anionic dye and therefore, relatively less

amount of dye (< 60%) was removed at alkaline pH. This observation was attributed

to electrostatic repulsion between adsorbate and adsorbent in excess of hydroxyl

ions which hindered the adsorption of CR anions on adsorbate. At acidic pH, the

positive charges (H+) at the solution interphase increased and the adsorbent surface

became more positively charged, thus electrostatic attraction of CR dye anions led to

high removal efficiency. More than 90 % dye removal was attained at pH = 7.0, pH =

10.0 and pH = 1.0 - 2.0 for MB, MG and CR dye respectively using CLP and ZMC

adsorbents.

19
3.4 Effect of adsorbent dose on dye adsorption

Adsorbent dose play a significant role in determining the adsorption capacity at a

given initial concentration of dye molecules in aqueous solution. Effect of adsorbent

dosage on removal of MB, MG and CR dyes was investigated for a wide range of

adsorbent amount (0.25 g to 2.5 g) in 100 mL solution of 10 mg/L dye concentration.

Results are shown here in Figure 5(A) and Figure 5(B) for CLP and ZMC adsorbent

respectively. Significant increase in percentage adsorption of dyes was observed

with increase in adsorbent dosage from 0.25 g to 2.5 g which can be attributed to the

increase in availability of adsorption sites on adsorbent surface with increase in dose

of the adsorbent. Maximum 99.6 % and 94 % of MB dye removal was obtained at

1.5 g dose of CLP and ZMC respectively. Significant removal of MG and CR was

observed at relatively lower adsorbent dose. Nearly 96 % MG dye was removed 0.5

g and 0.25 g of CLP and ZMC respectively. CR dye could not be removed more than

90 % using both adsorbents at optimum dose of the adsorbents i.e. 0.5 g and 1.25 g

of CLP and ZMC respectively. Further increase in adsorbent dosage did not show

significant increase in percentage removal of dye. Though, percentage removal of all

dyes increased with increase in adsorbent dosage, the equilibrium adsorption

capacity was observed to decrease with increase in the amount of adsorbent as

shown in Figure 5. This observation may be attributed to the overlapping or

aggregation of the adsorption sites [61,62] which decreases the total surface area of

adsorbent and thus, limits the availability of active sites during adsorption process

[17, 63].

Figure 5: Effect of adsorbent dose on adsorption capacity (mg/g) (red plots)

and (%) adsorption efficiency (black plots) of (A) CLP adsorbent (B) ZMC

20
Adsorbent (Initial conc. = 10 mg/L; agitation time = 30 min.; settling time = 1 h;

stirring speed = 150 rpm; pH = 7.0).

3.5 Possible Mass Transfer Limitations in Dye Adsorption Process

Possible internal and external mass transfer limitations for the proposed dye-

adsorbent systems were investigated on the basis of particle size distribution and

stirring speed respectively. Internal mass transfer resistance was assumed to be

negligible in present study due to very fine particle size distribution (<150 µm).

Verification of external mass transfer resistance was accomplished by varying the

stirring speed from 0 - 150 rpm at room temperature, agitation time 30 min. and initial

dye concentration 10 mg/L. Results are shown in Figure 6(A) and 6(B) for dye (MB,

MG, CR) removal using CLP and ZMC adsorbent respectively.

Figure 6: Effect of stirring speed on dye adsorption efficiency using (A) CLP

Adsorbent (B) ZMC Adsorbent (Initial conc.= 10 mg/L, contact time = 30 min,

settling time = 1 h, pH = 7.0).

More than 70 % dye adsorption efficiency was observed using both adsorbents even

when experiments were performed without stirring, though increase in dye removal

efficiency was attained with an increase in stirring speed. No any significant change

in adsorption efficiency was observed beyond a stirring speed of 50 rpm for CLP and

100 rpm for ZMC. Therefore, 50 rpm and 100 rpm were considered as the optimum

stirring speed for dye-CLP and dye-ZMC adsorbent systems respectively in order to

minimize external mass transfer resistance. Only 1 - 2 % improvement in adsorption

efficiency was observed with increase in stirring speed beyond the optimum stirring

speed as shown in Figure 6.

21
3.6. Adsorption Kinetic Studies

3.6.1. Effect of Agitation Time

Effect of agitation time on adsorption of MB, MG and CR dyes was studied at room

temperature (303 K) using CLP and ZMC green adsorbents and results are shown in

Figure 7(A) and Figure 7(B) respectively. A rapid removal was observed in first 5 - 10

min., followed by gradual adsorption process at slower rate which may be due to the

fact that initially all active sites were vacant and readily available for the adsorption of

dye ions from aqueous solution. Since the external surface is occupied by dye

molecules at earlier stages, slower adsorption rate at later stages can be explained

on the basis of diffusion of dye molecules into the interior area of the adsorbent.

Equilibrium stage was attained within 25 - 30 min. at initial dye concentration of 10

mg/L. No further increase in adsorption efficiency was observed, once the

equilibrium is attained. This observation can be attributed to the fact that remaining

vacant sites are difficult to occupy probably due to predominance of repulsive forces

between the molecules present on the adsorbents and in the bulk phase [64].

Results were found to be in concordance with the literature [61,62]. CLP adsorbent

removed 99 % MB dye in 20 min. whereas maximum 97 % MG removal was

observed in 30 min. using ZMC adsorbent. Nearly 89 % and 83 % CR removal

efficiency was observed using CLP and ZMC respectively in 30 min. agitation time.

Therefore, further batch experiments with all employed adsorbate-adsorbent

systems were conducted for 30 min. agitation time.

Figure 7: Effect of agitation time on dye adsorption efficiency using (A) CLP

Adsorbent (B) ZMC Adsorbent (Initial conc.=10 mg/L, settling time = 1 h, pH = 7.0,

stirring speed = 150 rpm).

22
3.6.2. Batch Kinetic Studies

Different kinetic models (pseudo first order, pseudo second order and elovich) were

employed in present study for the analysis of kinetic sorption data using linear

regression method. Linear plots for each kinetic model were drawn by employing

equation (2) – equation (4). Plots obtained for pseudo first order, pseudo second

order and elovich kinetic model are shown in Figure S-2 of supporting information.

Data points for pseudo first order model do not fit to a straight line whereas straight

lines and high values of correlation coefficient (R2) were obtained from data points of

pseudo second order kinetic model. Plots obtained for the data points of elovich

kinetic models also do not follow the linear regression analysis. Table 3 lists the

kinetic parameters obtained using the linear regression method for different kinetic

models. It can be inferred from Table 3 that correlation coefficient (R 2) approaches

unity for pseudo second order kinetic model while performing dye adsorption

experiments using CLP and ZMC adsorbents. The calculated qe,cal values obtained

from pseudo second order kinetic model was found to be in good agreement with

experimental values qexp and thus, indicated the applicability of pseudo-second order

kinetic model for CLP-MB, CLP-MG, CLP-CR, ZMP-MB, ZMP-MG and ZMP-CR

adsorption systems. Normalized standard deviation and (%) ARE have been

compared in order to find out the best fitted kinetic model. Results for error analysis

are also listed in Table 3. Least values of the normalized standard deviation Δq t (%)

and (%) ARE substantiate the pertinence of pseudo second order kinetic model for

all the employed adsorption systems.

23
3.6.3. Adsorption Mechanism

The proposed solid-liquid adsorption process is mainly carried out in three steps i.e.

external mass transfer, pore diffusion and reaction controlled process. External mass

transfer was neutralized in present study by maintaining optimum stirring speed

during adsorption experiments. Reaction controlled process is relatively rapid

process, therefore, it cannot be considered as the rate determining step. SEM

studies clearly indicated CLP and ZMC as porous materials as mentioned in section

3.2.3; therefore, it is important to investigate the role of pore diffusion in order to

ascertain it as a rate limiting step.

The experimental kinetic data was fitted to intraparticle diffusion model which is

given as equation (22) [65] :

𝑞𝑡 = 𝑘𝑑 𝑡1/2 + 𝐶 ………………(22)

kd (mg/g.min1/2) is the rate constant for intraparticle diffusion and C is the intercept

for the linear plot of qt versus t1/2 which reflects the boundary layer effect. Linear plot

of qt versus t1/2 is shown in Figure S-3 of supporting information for the three

employed dyes using CLP and ZMC adsorbent respectively and the kinetic

parameters are listed in Table 3. It was depicted from experimental observations

(Figure S-3) that intraparticle diffusion plots should be divided into two different linear

regimes: the linear segment during initial phase (first 5 min.) corresponds to

adsorption of dyes on the surface of adsorbent which can be referred as film

diffusion. Linear plot in the second regime for later time duration represented gradual

diffusion of dyes to adsorption site i.e. pore diffusion [30]. Thus, it was inferred that

removal of MB, MG and CR dyes using CLP and ZMC green adsorbents was

governed by film diffusion and pore diffusion mechanism. Values of correlation

24
coefficient (R2) indicated film diffusion as the more dominating mechanism than pore

diffusion in the present study. Results were found to be in good agreement with

literature for the removal of MG and MB using different low-cost adsorbents

[30,54,56].

3.7. Batch Equilibrium Studies

3.7.1. Effect of initial dye concentration

Equilibrium studies were conducted at optimum reaction conditions by varying the

concentration of dye from 5 mg/L to 25 mg/L in aqueous solution. Experiments were

performed at room temperature, stirring speed 150 rpm, pH 7.0 and agitation time 30

min. Results are shown in Figure 8(A) and Figure 8(B) for CLP and ZMC

respectively. It was observed that the removal efficiency of CLP and ZMC decreases

with an increase in initial concentration of dyes in synthetic solution, though the

actual amount of dye adsorbed per unit mass of adsorbent increased.

Figure 8: Effect of initial dye concentration on dye adsorption efficiency using

(A) CLP Adsorbent (B) ZMC Adsorbent.

The uptake of dye was increased from 0.06 to 1.62 mg/g, 0.17 to 4.70 mg/g, 0.17 to

3.77 mg/g using CLP with an increase in concentration of MB, MG, CR dyes

respectively. Increase in dye uptake may be attributed to an increase in the

concentration gradient with increase in initial dye concentration which provides a

driving force to minimize mass transfer resistances of dyes between the aqueous

and solid phase [56]. Percentage removal of dye decreased nearly 6 – 10 % for MB,

MG and CR dyes with increase in dye concentration of aqueous solution from 5 mg/L

to 25 mg/L for ZMC adsorbent.

25
3.7.2. Equilibrium Isotherms

Sorption isotherms represent the specific relation between the equilibrium

concentration of adsorbate in the bulk and the adsorbed amount at the surface [45].

Plots of langmuir, freundlich and D-R isotherm have been shown in Figure S-4 of

supporting information for all adsorption systems and calculated parameters have

been listed in Table 4. The linear plot of specific sorption (Ce/qe) against the

equilibrium concentration (Ce) demonstrate that sorption of MB on CLP and ZMC

follow the langmuir isotherm with the highest value of correlation coefficient R 2,

though the maximum adsorption capacity Q 0 was noted highest for MG dye (8.733

mg/g and 16.72 mg/g) using CLP and ZMC respectively.

Separation Factor (RL) was also calculated for langmuir isotherm using equation (9)

and is plotted in Figure 9. The RL values were found to be in the suggested range for

favourable adsorption i.e. 0 < RL < 1 at 303 K for all the employed adsorption

systems. It was also depicted from Figure 9 that RL value approaches zero with

increase in initial dye concentration (C0) which indicated less favourable adsorption

at high initial dye concentration.

Figure 9 : Variation of separation factor (RL) as a function of initial dye

concentration.

Experimental data obtained for MG and CR dye fitted well to the freundlich isotherm

with R2 > 0.97 whereas removal of MB dye using CLP adsorbent did not correspond

to freundlich isotherm. ZMC adsorbent was found to be suitable for the adsorption of

all three employed dyes (MB, MG and CR) with high value of R 2 ( > 0.995) and high

dye uptake capacity (Kf). Value of freundlich constant ‘n’ was found to be greater

than 1 for all adsorption systems and clearly indicated a favourable adsorption

26
process. The dye uptake capacity Kf was found to be the highest for MG-ZMC

system which inferred efficient adsorption of MG dye on Zea Mays cobs.

D-R isotherm was observed to be a well fitted model with high value of correlation

coefficient (R2 > 0.95) for all employed adsorption systems. Adsorption capacity (q m)

was again found to be maximum for MG using ZMC adsorbent. Value of mean

adsorption energy (E) lies between 8 - 16 kJ/mol for MB-CLP, MG-CLP, CR-CLP,

MB-ZMP, MG-ZMP and CR-ZMP adsorption system which suggested chemisorption

process for the present study.

3.8. Thermodynamics Studies

3.8.1. Effect of solution temperature of dye adsorption systems

Effect of solution temperature on the adsorption of MB, MG and CR dyes using CLP

and ZMC adsorbents was investigated by varying the solution temperature from 303

K to 333 K. Figure 10 demonstrates the increase in percentage adsorption of dyes

on CLP and ZMC with an increase in solution temperature under optimum reaction

conditions. This observation led to the conclusion that the proposed dye adsorption

may be considered an endothermic process. The increasing rate of dye removal may

be attributed to increase in rate of diffusion of the dye molecules across the external

boundary layer and into the internal pores of the adsorbent particles [52]. Results

were found to be in concordance with the literature data where adsorption of dyes

from aqueous solution was investigated using sepiolite [66], durian seed activated

carbon [52] and oat hull [30] as efficient adsorbents.

Figure 10 : Effect of solution temperature of dye adsorption systems.

3.8.2. Thermodynamic parameters

27
Van’t Hoff plot of ln(Kd) vs 1/T is shown in Figure 11 for all the adsorption system

employed in present study. Thermodynamic parameters (ΔH° and ΔS°) were

calculated from the slope and intercept of Van’t Hoff plot respectively using equation

(14). Table 5 summarizes the thermodynamic parameters determined at different

temperatures ranging from 303 K to 333 K. The positive value of ΔH° substantiated

the endothermic nature of the dye sorption process. The positive ΔS° values suggest

the increased randomness at solid-liquid interface and reflect favourable condition

for the removal of MB, MG and CR dyes from synthetic solutions.

Figure 11 : Van’t Hoff plot of ln (Kd) vs 1/T.

Gibbs free energy ΔG° was calculated using equation (15) and values are reported

in Table 5 at different solution temperatures. Negative values ΔG° indicated that

adsorption of dyes on CLP and ZMC adsorbents is feasible and spontaneous in

nature. Increase in values of ΔG° with increase in solution temperature depicts

higher temperature to be favourable for the dye adsorption. The thermodynamic

findings are in good agreement with the literature information for the adsorption of

dyes on different types of adsorbents.

4. Conclusion

Present study is a successful demonstration of the agricultural waste management

and application of novel green low-cost adsorbents for industrial waste water

treatment. Adsorption potential of green adsorbents CLP and ZMC was pioneered

for the removal of dyes (MB, MG, CR) from aqueous solutions. The process was

found to be highly dependent on solution pH, initial dye concentration, adsorbent

dose, agitation time and solution temperature. Characterization studies substantiated

the efficient adsorption of dyes on both adsorbents. The calculated qe,cal values

28
computed from pseudo second order equation showed good agreement with

experimental values qexp, and indicated the applicability of pseudo-second order

kinetic model for all the employed adsorption systems. The dye uptake process was

found to be controlled by intraparticle diffusion in two stages i.e. film diffusion at

earlier stages followed by pore diffusion after 5 min. agitation time. ZMC was

observed to be the most suitable adsorbent for adsorption of MB, MG and CR dyes

with highest dye uptake capacity. Thermodynamic studies indicated dye-CLP and

dye-ZMC adsorption systems as feasible, spontaneous and endothermic in nature.

Proposed low-cost adsorbents can be considered an environmentally benign

substitute of chemically modified adsorbents for the effective removal of toxic

components from industrial waste water.

29
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37
List of Tables :

Table 1 : Characteristics and Structure of the dyes MB, MG and CR

Table 2 : Proximate Analysis for Citrus Limetta peel and Zea Mays Cob

Table 3 : Kinetic Parameters and Error Analysis for Pseudo First Order,

Pseudo Second Order and Elovich Kinetic Models

Table 4 : Parameters for Langmuir, Freundlich and D-R isotherms

Table 5: Thermodynamic Parameters for dye adsorption on CLP and ZMP

adsorbent

38
List of Figures :

Figure 1 : Preparation of Low-cost adsorbents (A) CLP (B) ZMC.

Figure 2 : FTIR spectra of raw and dye loaded (A) CLP (B) ZMC adsorbent.

39
Figure 3 : SEM Images of (A) Fresh CLP (B) Fresh ZMC adsorbent.

40
Figure 4(A): Effect of solution pH on adsorption capacity (mg/g) (red lines)

and (%) adsorption efficiency of CLP adsorbent (black lines)

(Adsorbent dose : MB (1.5 g), MG (0.5 g), CR (0.5 g); Initial dye conc.

= 10 mg/L; agitation time = 30 min.; settling time = 1 h; stirring speed =

150 rpm).

41
Figure 4(B): Effect of solution pH on adsorption capacity (mg/g) (red lines) and

(%) adsorption efficiency of ZMC adsorbent (black lines)

(Adsorbent dose : (MB (1.5 g), MG (0.25 g), CR (1.25 g); Initial dye

conc. = 10 mg/L ; agitation time = 30 min.; settling time = 1 h; stirring

speed = 150 rpm).

42
Figure 5: Effect of adsorbent dose on adsorption capacity (mg/g) (red plots)

and (%) adsorption efficiency (black plots) of (A) CLP adsorbent

(B) ZMC Adsorbent (Initial conc. = 10 mg/L; agitation time = 30 min.;

settling time = 1 h; stirring speed = 150 rpm; pH = 7.0).

43
44
Figure 6: Effect of stirring speed on dye adsorption efficiency using (A)

CLP Adsorbent (B) ZMC Adsorbent (Initial conc.= 10 mg/L, agitation

time = 30 min, settling time = 1 h, pH = 7.0).

Figure 7: Effect of agitation time on dye adsorption efficiency using (A) CLP

Adsorbent (B) ZMC Adsorbent (Initial conc.=10 mg/L, settling time =

1 h, pH = 7.0, stirring speed = 150 rpm).

45
Figure 8: Effect of initial dye concentration on dye adsorption efficiency

using (A) CLP Adsorbent (B) ZMC Adsorbent (agitation time = 30

min, settling time = 1 h, pH = 7.0, stirring speed = 150 rpm)

46
47
Figure 9 : Variation of separation factor (RL) as a function of initial dye

concentration.

Figure 10 : Effect of solution temperature of dye adsorption systems.

48
Figure 11 : Van’t Hoff plot of ln (Kd) vs 1/T.

49
Table 1 : Characteristics and Structure of the dyes MB, MG and CR

Malachite Green
Characteristics Methylene Blue Congo Red
Oxalate

Manufactures Qualikems India Fisher Scientific CDH

Pvt. Ltd.

Class cationic thiazine cationic N-methylated anionic benzedene

dye diamino triphenyl dye

methane dye

Molecular Formula C16H18N3SCl.xH2O C52H54N4O12 C32H22N6Na2O6S2

Molecular Weight 319.85 927.02 696.67

Wavelength (λmax) 662 nm 616 nm 499 nm

Table 2 : Proximate Analysis for Citrus Limetta peel and Zea Mays Cob

Properties Temp. (°C) Time (min) Citrus Limetta Zea Mays

Moisture (%) 105 90 8.9 6.2

Ash (%) 650 30 3.1 1.9

Volatile Matter (%) 910 7 75.8 78.4

Carbon (%) 12.2 13.5

50
 Table 3 : Kinetic Parameters and Error Analysis for Pseudo First Order,

Pseudo Second Order and Elovich Kinetic Models

Kinetic CLP ZMC

Parameter
Model Methylene Malachite Congo Methylene Malachite Congo
s/ Error
Blue Green Red Blue Green Red
Analysis

qcal 0.535 0.827 0.648 0.236 0.465 0.061

qexp 0.664 1.930 1.660 0.752 3.909 0.722

Pseudo k1 0.253 0.194 0.122 0.169 0.147 0.081

First Order R2 0.983 0.911 0.763 0.944 0.969 0.935

∆qt (%) 6.12% 19.8% 21.04% 23.9% 31.0% 32.2%

% ARE 14.8% 49.9% 52.9% 60.2% 78.1% 81.1%

qcal 0.676 1.942 1.692 0.766 3.940 0.725

qexp 0.664 1.930 1.660 0.752 3.909 0.722

Pseudo H 1.213 6.377 2.310 1.364 15.948 2.355

Second k2 2.656 1.6901 0.806 2.321 1.027 4.473

Order R2 0.999 0.999 0.999 0.999 0.999 0.999

∆qt (%) 2.66% 3.85% 3.81% 2.18% 1.12% 1.26%

% ARE 4.52% 9.43% 9.33% 4.16% 1.96% 2.32%

Α 3.1E+03 6.3E+08 4.8E+09 1.38E+05 4.70E+11 8.04E+09

Β 21.8 13.64 11.50 24.509 8.278 41.666

Elovich
R2 0.905 0.913 0.9203 0.978 0.913 0.948
Model
∆qt (%) 7.44% 4.08% 10.10% 5.84% 3.31% 3.59%

% ARE 18.3% 10.04% 25.46% 14.4% 8.13% 8.82%

Intraparticle kd1 1.4825 0.3117 0.288 0.245 0.747 0.5232

(Film C1 0.0842 0.0185 0.042 0.0256 0.0925 0.0811
Diffusion)
R2 0.992 0.987 0.943 0.973 0.964 0.946

Intraparticle kd1 0.0155 0.0571 0.0115 0.0189 0.0276 0.0444

(Pore C1 0.6664 3.5966 0.655 0.559 1.7696 1.401
Diffusion)
R2 0.958 0.8134 0.8695 0.9151 0.9173 0.960

51
 Table 4 : Parameters for Langmuir, Freundlich and D-R isotherms

Kinetic CLP ZMC

Paramete
Isotherm Methylen Malachite Congo Methylene Malachite Congo
rs/ Error
e Blue Green Red Blue Green Red
Analysis

Q0 6.361 8.733 6.596 4.440 16.72 8.417

Langmuir
B 1.122 0.811 0.216 0.267 0.593 0.276
Isotherm
RL 0.47-0.03 0.55-0.04 0.82-0.15 0.78-0.13 0.62-0.063 0.78-0.12
R2 0.994 0.978 0.984 0.992 0.974 0.974

N 2.606 1.388 1.490 1.212 1.170 1.390

Freundlich
Kf 2.070 3.907 1.179 0.909 6.884 1.749
Isotherm
2
R 0.939 0.974 0.994 0.995 0.996 0.995

Dubinin- Β 0.002 0.004 0.007 0.006 0.004 0.006

Radhu- qm 2.574 8.536 4.553 2.652 12.84 5.687
kevich E 15.81 11.18 8.451 9.128 11.18 9.128
Isotherm R2 0.959 0.996 0.972 0.997 0.999 0.978

Table 5: Thermodynamic Parameters for dye adsorption on CLP and ZMP

adsorbent

Adsorbents Dye ΔH° ΔS° ΔG° (kJ/mol)

(kJ/mol) (J/mol/K) 303K 313K 323K 333K

CLP MB 10.8 65.2 - 8.96 - 9.61 -10.26 -10.92

MG 25.7 106.2 - 6.41 - 7.48 - 8.54 - 9.60

CR 6.38 28.8 - 2.36 - 2.64 - 2.93 - 3.22

ZMP MB 12.8 61.1 - 5.66 - 6.28 - 6.89 - 7.50

MG 13.1 67.5 - 7.36 - 8.03 - 8.71 - 9.38

52
CR 14.1 60.9 - 4.30 - 4.91 - 5.51 - 6.12

53