Accepted Manuscript

Design, characterization and appraisal of chemically modified

polysaccharide based mucilage from Ocimum basilicum (basil)
seeds for the removal of Cd(II) from spiked high-hardness ground
water

Bilal Ahmad Lodhi, Azhar Abbas, Muhammad Ajaz Hussain,

Syed Zajif Hussain, Muhammad Sher, Irshad Hussain

PII: S0167-7322(18)33499-8
DOI: doi:10.1016/j.molliq.2018.10.056
Reference: MOLLIQ 9801
To appear in: Journal of Molecular Liquids
Received date: 7 July 2018
Revised date: 8 October 2018

Please cite this article as: Bilal Ahmad Lodhi, Azhar Abbas, Muhammad Ajaz Hussain,
Syed Zajif Hussain, Muhammad Sher, Irshad Hussain , Design, characterization and
appraisal of chemically modified polysaccharide based mucilage from Ocimum basilicum
(basil) seeds for the removal of Cd(II) from spiked high-hardness ground water. Molliq
(2018), doi:10.1016/j.molliq.2018.10.056

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 ACCEPTED MANUSCRIPT

Design, characterization and appraisal of chemically modified polysaccharide based

mucilage from Ocimum basilicum (basil) seeds for the removal of Cd(II) from spiked high-

hardness ground water

Bilal Ahmad Lodhi, Azhar Abbas, Muhammad Ajaz Hussain*, Syed Zajif Hussain,

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Muhammad Sher, Irshad Hussain

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B. A. Lodhi, A. Abbas, M. A. Hussain, M. Sher

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Ibn-e-Sina Block, Department of Chemistry, University of Sargodha, Sargodha 40100, Pakistan
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S. Z. Hussain, I. Hussain

Department of Chemistry, SBA School of Science & Engineering, Lahore University of

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Management Sciences, Lahore Cantt 54792, Pakistan

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E-mail: majaz172@yahoo.com (M.A. Hussain)

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Abstract

Ocimum basilicum L. seed mucilage (OBM) was separated mechanically and esterified to form

OBM succinate (OBMS) and sodium salt of OBM succinate (Na-OBMS). These products were

then exploited for Cd(II) removal from spiked high hardness ground water (HGW) and distilled

water (DW) solution. Na-OBMS was characterized by FT-IR (Fourier-transform infrared

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spectroscopy), SEM-EDS (scanning electron microscopy-energy dispersive spectroscopy), zero-

point charge pH and solid-state CP/MAS 13C NMR (nuclear magnetic resonance spectroscopy).

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Na-OBMS was found to be a good sorbent for Cd(II) removal from DW and HGW. Effects of

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pH (1-7), temperature (290-343 K), interaction time (5-120 min) and sorbent dose (10-60 mg) on

sorption capacity of the sorbent Na-OBMS were investigated. Negative values of different
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thermodynamic parameters (∆G°, ∆S°, and ∆H°) indicated the exothermic and spontaneous
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nature of sorption. Different isothermal and kinetic models were applied on sorption data.

Langmuir isothermal model and pseudo second order kinetic model provided best fit to the
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experimental sorption data. Maximum sorption capacity of Na-OBMS for Cd(II) uptake as
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determined by Langmuir isothermal model was found as 443.06 and 405.63 mg g-1 for DW and

HGW, respectively. The sorbent was recovered simply by treating with brine and utilized again
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for sorption. A negligible decrease (9.5 and 11.4% for DW and HGW, respectively) was found in
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the efficacy of sorbent after five cycles of recovery.

Keywords: Ocimum basilicum mucilage, Cd(II) uptake, Bio sorbent, Regenerability, Ion-

exchange

1. Introduction

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One of the major environmental issues is the contamination of water (ground and surface) by

toxic heavy metals like lead, cadmium, mercury, etc. Such type of toxic substances pollute water

as a result of human, animal and biological activities [1,2]. These heavy metals are the natural

components of earth crust and occur in dissolved or colloidal state in water. These are persistent

environmental pollutants and do not degrade [3,4]. Cadmium is one of the toxic metals even at

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low concentration and is released from different sources like unplanned industrialization [5],

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inappropriate disposal of municipal waste water, mining activities, combustion of fossil fuels,

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and most commonly by rechargeable battery industries [6-8]. According to world health

organization (WHO), the maximum acceptable limit for cadmium in drinking water is 0.003

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mg/L which bio-accumulates when enters into human body and causes many disorders if
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exceeds the limit [9]. Cadmium, affects the cellular functions of proteins [10], causes bone

demineralization [11], causes lungs and renal cancer [12], hypertension [9] and interact with
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enzymes to form biotoxic compounds [6].

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To clean up the water from toxic metals, a wide variety of techniques are available, i.e.,
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reverse osmosis [13], adsorption [14], filtration [15], electrochemical and chemical precipitation

[16], chelation [17] and ion exchange [18]. Ion-exchange method is considered best among the
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various methods of water treatment due to its rapidity, selectivity, efficiency and regenerability.
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Chemical methods for heavy metal removal are of high cost, causes environmental pollution and

are less effective as compared to ion exchange [18].

Natural cellulosic materials such as plant barks, fruit peels agriculture wastes, algae and

fungi, etc., are low cost sorbent materials for toxic heavy metal removal from water resources

[19-23]. Furthermore, such sorbents without any chemical modification exhibit moderate or even

low sorption capacity values to remove toxic metals while chemically modified plant waste

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matter [24] show high adsorption capacity [25]. It is also possible to modify the polysaccharides

containing hydroxyl groups by using anhydrides of carboxylic acid [26] and products obtained

may contain some ions which tend to exchange the ions of heavy metal in solutions [27].

Ocimum basilicum L., generally known as sweet basil is a popular culinary and ornamental

herb. Upon soaking in water, it swells rapidly and extrudes mucilage [28,29]. This mucilage of

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Ocimum basilicum contains carbohydrates like D-Glucose, D-Galactose, D-Mannose, L-

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Rhamnose, glucomannan, pectins, hemicellulose materials, and little amount of non-

polysaccharides like protein, minerals and fat [30]. Due to hydroxyl functional groups (-OH)

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present in the OBM, it is possible to carry out chemical modification by different methods such

as esterification and the new materials obtained can be utilized as sorbent for heavy metal
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removal such as cadmium removal from water.
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Herein, we report the synthesis of succinylated OBM (OBMS) by esterification of OBM

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using succinic anhydride and conversion of as synthesized OBMS into its sodium salt (Na-

OBMS) by treating with saturated solution of NaHCO3. These OBMS and Na-OBMS are utilized
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as unconventional sorbent materials for the removal of Cd(II) from distilled water (DW) and
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spiked high hardness ground water (HGW) by ion exchange method. Effect of different factors

(pH, time, sorbent dose, initial concentration and temperature) on removal of Cd(II) from
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aqueous solution is studied. Repeated use of the sorbent after regeneration by treating with brine

is also studied.

2. Materials and methods

2.1. Materials

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Basil seeds were purchased from the local market. Analytical grade succinic anhydride, 4-

dimethylaminopyridine, cadmium nitrate, ethanol, n-hexane, sodium bicarbonate, hydrochloric

acid and sodium hydroxide provided by Fluka. Hard ground water (HGW) samples collected

from district Sargodha (Pakistan) and nearby area and some basic analysis were carried out by

typical water analysis methods, i.e., total hardness as CaCO3 (1430 mgL-1), Ca+2 hardness (338

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mgL-1), Mg+2 hardness (1090 mgL-1), Cl-1 hardness (1410 mgL-1) and pH 7.3.

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2.2. Isolation of seed-mucilage

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Seeds of Ocimum basilicum (100 g) were soaked in deionized water (DW) (1000 mL) for 4 h and
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then warmed at 40 °C for 45 min. The extruded Ocimum basilicum seed’s mucilage (OBM) was

separated by a cotton cloth and washed with de-ionized water and de-fatted with n-hexane (three
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times) to make it free from non-polar impurities. A further washing with ethanol was given to
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remove polar fractions in mucilage, if any. It was then dried under vacuum. After drying, it was

ground, passed through No. 60 mesh sieve and stored.

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2.3. Synthesis of Ocimum basilicum mucilage-succinate (OBMS)

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The OBM (2.0 g) suspension was prepared in N,N-dimethylacetamide (DMAc) by stirring for 60

min at 353 K under nitrogen environment. Succinic anhydride (7.4 g) and catalyst

dimethylaminopyridine, (DMAP 100 mg) were then added into the suspension with stirring

continuously at 353 K for 8 h. Then the reaction mixture containing OBMS conjugate was

precipitated in ethanol (250 mL) and washing of precipitates was carried out thrice with ethanol

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to make product free from succinic acid and unreacted succinic anhydride. The precipitates were

dried in a vacuum desiccator and ground into powder form.

DS of succinyl moieties = 1.10; Yield = 81 %

FTIR: 3271-3588 cm-1 (O-H), 2916 cm-1 (C-H), 1722 cm-1 (C=OEster) and 1040 cm-1 (C-O-C).

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2.4. Synthesis of sodium salt of OBMS (Na-OBMS)

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A saturated aq. solution of NaHCO3 was prepared and powdered OBMS conjugate was stirred

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with it for 2 h at room temperature to synthesize Na-OBMS, i.e., sodic form of OBMS. This

suspension was then filtered to get solid Na-OBMS which was thoroughly washed with distilled
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water until pH of the distilled water becomes neutral. The sorbent Na-OBMS was observed to
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form particulate solid suspension in water.

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FTIR: 3219-3586 cm-1 (O-H), 2922 cm-1 (C-H), 1730 cm-1 (C=OEster), 1574 cm-1 (COO-), 1040

cm-1 (C-O-C)
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2.5. Characterization of OBMS and Na-OBMS

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2.5.1. Spectroscopic analyses

The FTIR (KBr) spectra of OBMS and Na-OBMS were recorded on IR-Prestige-21 (Shimadzu,

Japan) using KBr pellet technique in the range of 4000-400 cm-1. The solid-state CP/MAS
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CNMR spectra of OBM, ONBMS and Na-OBMS sorbent was acquired by using Bruker DRX-

400 machine at following parameters: ambient temperature, 100 MHz, NS 5000, acquisition time

0.32 s, delay time 2 s, pulse time 4.85 s, proton 90o. To determine the concentration of Cd(II)

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ions from supernatant, flame atomic absorption spectrophotometer (FAAS, AA 6300, Shimadzu,

Japan) was used at 228.8 nm by using air-acetylene flame.

2.5.2. Scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS)

The SEM and EDS analyses of products, i.e., OBMS and Na-OBMS were performed before and

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after Cd(II) uptake. Samples were dried over separate aluminum stubs. The electron microscope

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(Nova, NanoSEM 450) furnished with low energy detector named Everhart-Thornely detector

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and Oxford Energy Dispersive X-ray (EDX) was used for this purpose.

2.5.3. Determination of zero-point charge pH (pHZPC)

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It is important to determine zero-point charge pH (pHZPC) to study sorption behavior of the
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sorbent. Solid addition method [31] was used to determine pHZPC for the Na-OBMS sorbent. For

this, Na-OBMS (20 mg) was kept in NaNO3 solutions (50 mL) with initial pH (pHi) values
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adjusted between 1 to 7 by adding 0.1 M HNO3 and shaken for 2 h at 150 RPM at 298 K. After
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filtration the final pH (pHf) values of the supernatant solutions were noted. The pHi values were
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plotted against pHf - pHi and a curve is obtained. This curve intersects the X-axis at some

specific value of pHi. This value of pHi is called pHZPC. At pHZPC the surface of the sorbent
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becomes neutral. Surface of the sorbent will be negatively charged if the pH value of the solution
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containing heavy metal ions will be greater than pHZPC, and it will be positively charged at pH

lower than pHZPC.

2.5.4. Determination of degree of substitution (DS)

DS of acidic form of newly synthesized sorbent i.e., OBMS is determined by stirring 100 mg of

it in 100 mL of NaHCO3 solution for about 2 h at 298 K [32]. After 2 h, the suspension was

filtered and a known volume of filtrate i.e., sodium bicarbonate (NaHCO3) solution was titrated

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against hydrochloric acid (HCl) (0.02M). Methyl orange was used as indicator. From this

titration, the volume of HCl required for the neutralization of NaHCO3 was determined. This

volume of HCl was used for the determination of DS of OBMS with the help of following (Eq.

2) relation;

𝑛𝐶𝑂𝑂𝐻 = 𝑉𝑁𝑎𝐻𝐶𝑂3 × 𝑀𝑁𝑎𝐻𝐶𝑂3 − 𝑉𝐻𝐶𝑙 × 𝑀𝐻𝐶𝑙 (Eq. 1)

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276.14×𝑛𝐶𝑂𝑂𝐻
𝐷𝑆 = 𝑚 (Eq. 2)
𝑂𝐵𝑀𝑆 −100×𝑛𝐶𝑂𝑂𝐻

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where mOBMS is the mass of OBMS, nCOOH is the number of moles of carboxylate i.e., succinate

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moieties conjugated with OBMS. DS of OBMS indirectly gives us number of exchangeable

sodium ions in the sodic form of the sorbent (Na-OBMS). DS of succinyl moieties on to OBM
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(as per anhydroglucose unit) was calculated to be 1.10.
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2.5.5. Calculation of yield

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Efficiency of the reaction is calculated by calculating theoretical yield of OBMS by following

equation [33];
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𝑚𝑂𝐵𝑀
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑌𝑖𝑒𝑙𝑑 = 𝑚𝑂𝐵𝑀 + (𝑀𝑤 𝑜𝑓 𝑂𝐵𝑀 × 𝐷𝑆 × 𝑀𝑆𝑢𝑐 ) (Eq. 3)
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where mOBMS is mass of polymer used for reaction, Mw of OBM denotes the mass of OBM
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repeating unit, DS is the degree of substitution of succinate moiety and MSuc is molar mass of

succinic acid. The percentage yield therefore was found to be 81%.

2.6. Removal of Cd(II) by Na-OBMS sorbent

The amount of sorbent was optimized by introducing powdered Na-OBMS 10, 20, 30, 40, 50

and 60 mg to Cd(II) (80 mg L-1) solutions while stirring at 298 K for 30 min at 140 rpm in both

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DW and HGW solutions. To develop ideal pH for Cd(II) uptake, the optimized amount of the

sorbent (20 mg) was stirred with Cd(II) (80mgL-1) solutions of HGW and DW by adjusting the

pH 1-7 using 1M solution of each NaOH and HNO3.

The initial concentration effect on sorption was assessed by stirring 20 mg of sorbent in both

HGW (100 mL) and DW (100 mL) containing 40, 60, 80, 100, 120, 140 and 160 mg L-1 of

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Cd(II) for 30 min at 140 rpm. The equilibrium concentrations of Cd(II) metal was analyzed by

FAAS. The sorption capacity and Cd(II) uptake by Na-OBMS was calculated by applying

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following equations (Eq. 4 and 5).

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𝐶𝑖− 𝐶𝑒
𝑞𝑒 = 𝑋 𝑉 (4)
𝑚
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𝐶𝑖− 𝐶𝑒
% 𝑢𝑝𝑡𝑎𝑘𝑒 = 𝑋 100 (5)
𝐶𝑖

where Ci is initial concentrations in mg L-1, Ce is equilibrium concentrations of Cd(II) in mg L-1

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and qe is equilibrium sorption capacity in mg g-1, V is the solution volume in L and m is the mass
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of Na-OBMS in g.
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The interaction time effects were observed by agitating optimized amount of sorbent (20 mg)
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over a time range of 5-120 min in HGW (100 mL) and DW (100 mL) solutions containing Cd(II)

(80 mg L-1) at 140 rpm, 298 K. The solutions were then filtered and filtrate was analyzed using
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FAAS.

The effect of temperature on sorption capacity of Na-OBMS was also studied over a

temperature range of 298-343 K. An optimized dose of sorbent was stirred with samples of

HGW (100 mL) and DW (100 mL) containing 80 mg L-1 of Cd(II) and the percentage of Cd(II)

uptake was measured by using FAAS after filteration.

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2.7. Determination of thermodynamics parameters

Different thermodynamic parameters like change in free energy (∆G°), entropy (∆S°), and

enthalpy (∆H°) were also determined by observing temperature effects on Cd(II) adsorption.

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Following equations were used (Eq. 6-8).

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𝐶𝑎𝑑𝑠
𝑘𝑐 = (6)
𝐶𝑒

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∆𝑆° ∆H°
ln𝑘𝑐 = − (7)
𝑅 𝑅𝑇

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∆𝐺° = −𝑅𝑇 ln ln𝑘𝑐 (8)

Where, Cads (mg L-1) is the amount of metal sorbed, Ce (mg L-1) is the equilibrium concentration
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of metal ion, Kc is the sorption equilibrium constant.
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2.8. Recovery of sorbent

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Regeneration studies were also carried out to check the efficiency of the sorbent. For this

purpose, the sorbent (20 mg) was stirred in Cd(II) solution (80 mg L-1) for 40 min and Cd(II)
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uptake by sorbent was then measured by FAAS. All the Cd(II) ions sorbed by sorbent were
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desorbed by agitating with brine solution (100 mL) for 24 h. The recovered sorbent was then

filtered, washed with DW until it gives a negative AgNO3 test, air dried and reused again for

metal uptake. These sorption-desorption studies were carried out over five cycles.

All the experiments were performed in triplicates and the concurrent values were taken to present

results.

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3. Results and discussion

3.1. Synthesis and characterization of products

3.1.1. Synthesis and FT-IR spectroscopic studies of OBMS and Na-OBMS

OBMS conjugate was synthesized under homogenous reaction conditions in which succinic

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anhydride was used as a reagent and DMAP (4-dimethylaminopyridine) as a catalyst. To

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increase the ion exchange capability, OBMS was converted into Na-OBMS by treating with

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saturated solution of sodium bicarbonate. Yield of OBMS conjugate was 81% and degree of

substitution (DS) of succinic acid functionalities on to OBM was 1.10 when calculated per

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anhydro-glucose repeating unit [34]. Fig. 1 shows the schematic diagram of synthesis of OBMS and
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Na-OBMS.
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OH

C1-C6
n

HO OH
OBM
= Repeating sugar units
Succinic anhydride
DMAP 353 K, 24 h

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OCOCH2CH2COOH

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C1-C6
n

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RO OCOCH2CH2COOH
OBMS
R= H or succinyl moiety
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NaHCO3
RT, 2 h
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OCOCH2CH2COONa
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C1-C6
n

RO OCOCH2CH2COONa
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Na-OBMS
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Fig. 1. Schematic diagram for the synthesis of OBMS and its conversion to Na- OBMS.

The appearance of distinct peak of carbonyl at 1722 cm-1 in FT-IR spectrum of OBMS
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illustrates the succinate formation. Furthermore, after the formation of sodium salt of OBMS,

this signal transferred to a higher value of 1730 cm-1 and a typical peak at 1574 cm-1 confirms the

presence of carboxylate anion [33-34]. All the characteristic polymer signals were also present in

spectra. For example, hydroxyl groups absorbed at 3416, 3271-3588 and 3219-3586 cm-1

whereas COC (glycosidic linkage) appeared at 1043, 1040 and 1040 cm -1 in OBM OBMS and

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Na-OBMS, respectively. FT-IR (KBr) spectra in Fig. 2 showed the desired modifications of

OBM to OBMS and Na-OBMS.

OBM

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OBMS

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OH
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Na-OBMS
CO Ester
COO-
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COC

4000 3500 3000 2500 2000 1750 1500 1250 1000 750 500
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Wavenumber, cm-1
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Fig. 2. Overlay FT-IR (KBr) spectra of OBM, OBMS and Na-OBMS.

3.1.2. Solid-state CP/MAS 13C NMR spectroscopic studies

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Fig. 3 shows the solid-state CP/MAS 13C NMR spectrum of OBM, OBMS and Na-OBMS which

confirms the success of esterification and formation of sodium salt. In spectrum of OBMS, ester

carbonyl signals (C7) appeared at 174.43 whereas terminal carbonyl of COOH group (C10)

appeared at 177.81 ppm. Sodic form of the sorbent (Na-OBMS) showed carbonyl of COONa

(C10) signals centered at 180.71 whereas its ester carbonyl appeared at 174.85 ppm. The

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repeating unit-sugars of OBM are also recognizable in all spectra. Carbons of succinyl moieties

C8 & C9 appeared at 29.80 & 32.23 and at 30.99 & 32.29 ppm for OBMS and Na-OBMS,

respectively as observed in reference [34]. Polymer (sugars) backbone signals appeared at

104.42, 105.05 & 104.68 for C1, 62.29-64.33, 62.55-64.87 & 61.39-64.90 for C6 and 71.81-

88.43, 71.11-88.96 & 71.84-88.80 for C2-5 in OBM, OBMS and Na-OBMS spectra,

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respectively.

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C2-5
OH

C 1 -C 6
n C1

HO OH C6
OBM
= R e p e a tin g s u g a r u n its

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OCOCH 2 CH 2 COOH

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C2-5
C1-C6
n
7 8 9 10

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RO OCOCH 2 CH 2 COOH
OBMS C1
R= H or succinyl moiety
C6 C8,9
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C10 C7
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O
COC
HC
2HC
2OO
Na
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C2-5
C
1-
C 6
n
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R
O OC
OCH
2C
HC
2OO
Na
C1
Na
-OB
MS
C6 C8,9
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C10
C7
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Fig. 3. Solid-state CP/MAS 13C NMR spectrum of OBM, OBMS and Na-OBMS.

3.1.3. SEM and EDS studies

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Surface morphology of the products OBM, OBMS and Na-OBMS as well as of Na-OBMS after

Cd(II) uptake was analyzed by means of SEM (Fig. 4a-d) / EDS (Fig. 4e-h). It was observed

from Fig. 4a-d that the surfaces are irregular, lumpy and inhomogeneous for all said samples.

The evidence for the existence of Na ions on sorbent as well as their exchange with Cd(II) ions

was confirmed by EDS analysis as represented in Fig. 4g and Fig. 4h, respectively.

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e) a)

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f) b)
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g) c)
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h) d)

Fig. 4. SEM images (a-d) and EDS spectra (e-h) of OBM, OBMS, Na-OBMS and Cd(II)-OBMS.

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3.1.4. Determination of zero-point charge pH

The pHZPC was determined to monitor charge on surface of sorbent with change in pH by a

known method. The pHZPC for Na-OBMS sorbent was found as 4.6 (Fig. 5). It is inferred that the

value above pHZPC greatly favors the sorption due to deprotonation of functional groups creating

negative charge on surface of sorbent [31, 33].

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1

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0.5
pHi-pHf

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0
0 1 2 3 4 5 6 7
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-0.5

-1
M

pHi
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Fig. 5. Zero-point charge pH (pHzpc) of Na-OBMS.

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3.2. Sorption studies for Cd(II) removal

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3.2.1. Effect of pH
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The surface charge and degree of ionization of sorbent is strongly dependent on the pH of the

metal ion solution. The effect of pH on the sorption capacity of Na-OBMS was investigated by

adding the sorbent into 100 mL of Cd(II) solution in both DW and HGW having a range of pH

from 1 to 7 and stirring the mixture at 200 rpm at 298 K. The influence of pH on removal of

cadmium metal was also investigated by shaking the sorbent with metal ion solution. Results

revealed that a negligible amount of metal ions was sorbed at highly acidic pH while a prominent

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increase in sorption occurred by increasing the pH (Fig. 6). At pH range of 4.6-7.0, an

instantaneous increase in sorption was noted and maximum sorption occurred at pH 6.0. As the

pH becomes greater than pHZPC, deprotonation of functional groups resulted negative charge at

sorbent surface which favors Cd(II) uptake. At pH < pHZPC, protonation of Na-OBMS takes

place and surface of the sorbent becomes positively charged resulting in less uptake of metal

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ions.

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As the pH is increased from values of pH corresponding to maximum metal uptake, the

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partial hydrolysis of metal ions occurs resulting in the formation of precipitate in the form

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hydroxide of Cd(II), i.e., Cd(OH)2 due to which concentration of metal ions decreases in the

solution which in turn decreases the sorption capacity. To avoid this possible and uncontrolled
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precipitation effect, pH values corresponding to maximum metal-uptake for Cd(II) is optimized
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for all other batch sorption experiments. Similar behavior has been reported by Singh et al. [35]

and Gupta et al. [36] for the sorption of Cd(II).

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400
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350 DW
HGW
Sorption capacity, mgg-1

300
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250
200
150
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100
50
0
1 2 3 4 5 6 7
pH

Fig. 6. Effect of pH on sorption capacity of Na-OBMS sorbent (sorption conditions: sorbent dose

= 20 mg in 100 mL Cd(II) solution, Cd(II) concentration both in DW and HGW = 80 mg L–1,

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temperature = 298 K, contact time = 30 min, pH was changed from 2 to 7 for both DW and

HGW).

3.2.2. Effect of sorbent dosage

In order to evaluate the minimum amount of sorbent which can remove maximum amount of

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sorbate i.e., Cd(II) ions, different sorbent quantities ranging from 10 to 60 mg of Na-OBMS

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were added to 100 mL of 80 mg L-1 solutions of Cd(II) in both DW and HGW. Optimal dosage

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was selected that was associated with maximum sorption capacity by the Na-OBMS sorbent. It

was noticed that the sorption capacity first increases then decreases with increase in sorbent

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dosage in HGW and DW samples (Fig. 7a). In fact, as the dosage increases, the exchange sites

on the sorbent surface remain unsaturated which lowers the sorption capacity. Moreover, the
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aggregation of the sorbent was also responsible for the decrease in sorption capacity. It is
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revealed from the studies that an optimum dosage for maximum sorption is 20 mg. Therefore,
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Na-OBMS is considered as a good sorbent and it can be a utilized for Cd(II) removal from DW

and HGW.
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3.2.3. Optimization of initial metal ion concentration

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The effect of initial metal ion concentration on sorption capacity of the sorbent is used to
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establish sorption isotherm. The studies for optimization of initial metal ion concentration

revealed that the sorption capacity increases by increasing the metal ion concentration until a

saturation in sorption capacity was observed at 80 mg L-1 for Cd(II) as shown in Fig. 7b. Here,

we can infer that as concentration of Cd(II) increases, more exchange of ions takes place with

sorption sites of the sorbent which results in high sorption capacity. It is also evident from the

plot, the sorption capacity of sorbent increases with increase in initial metal ion concentration in

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start but after a certain metal ion concentration is reached, it becomes constant. This can be

attributed to presence of more number of exchange sites i.e., Na+ ions in the sorbent at the start

available for exchange with metal ions but later on when all these sites were occupied the

sorption capacity becomes constant.

3.2.4. Effect of interaction time

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Effect of contact time on sorption capacity of the sorbent is studied in order to decide about

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kinetics and mechanism of sorption process. The optimized amount of sorbent (20 mg) at

optimum pH showed a maximum Cd(II) uptake from samples of DW and HGW within first 20

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min. Fig. 7c shows that the metal sorption first increased and then became constant until an

equilibrium was achieved. A lot of metal exchange sites present initially are responsible for fast
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sorption in first 20 minutes and 96.5% and 93.5% of Cd(II) was removed from DW and HGW,
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respectively within this short time. As the time goes on, the sorbent sites were unable to sorb
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remaining Cd(II) due to repulsive forces between metal ions and aqueous media (see Fig 7c).

3.2.5. Effect of temperature

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Effect of temperature on sorption capacity of sorbent is examined to predict the thermodynamic

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nature of sorption process. As temperature is increased from 298 to 343 K, sorption capacity of

the sorbent i.e., Na-OBMS for Cd(II) uptake was found to decrease by 35 and 30 mg g-1 for
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HGW and DW solutions, respectively. Hence, it was inferred that the process of sorption was

exothermic in nature (Fig 7d). The reason for high sorption capacity at low temperature might be

more interaction of Cd(II) with the sorbent sites whereas at high temperature, kinetic energy and

transport of ions increases causing less attraction between sorbent and metal ions and resulting in

low sorption capacity.

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500

450 (a) (b)

Sorption capacity (mg g-1 )

Sorption capacity (mg g-1 )

400

300
300

150

T
200
DW HGW DW HGW

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0 100
0 15 30 45 60 0 30 60 90 120 150 180

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Sorbent dose, mg Concentration (mg/L)
450 450
(d)
(c)
Sorption capacity (mg g-1 )

Sorption capacity(mg g-1)

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300 AN 350

150 250

DW HGW DW HGW
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0 150
0 30 60 90 120 290 310 330 350
t, min T, K
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Fig. 7. a) Sorbent dosage effect (10-60 mg), b) Initial metal ion concentration effect (40-160 mg
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L-1 ), c) interaction time effect (5-120 min) and d) Temperature effect (298-343 K) on sorption

capacity of Na-OBMS (optimum sorption conditions: sorbent dose = 20 mg in 100 mL Cd(II)

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solution, Cd(II) concentration both in DW and HGW = 60 mg L–1, temperature = 298 K, contact
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time = 30 min, pH was kept at 6.0 for both DW and HGW).

3.2.6. Isothermal studies

Isothermal studies were carried out to observe sorbed species allocation between the sorbent and

sorbate at equilibrium. This study also predicts about the value of sorption capacity. Freundlich

and Langmuir isothermal models were employed to describe the experimental data of Cd(II)

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sorption. The later method provided best fit for Cd(II) sorption data. While Freundlich isotherm

could not provide best fit. So, Langmuir isothermal model was used to apply experimental data.

The linear form of Langmuir isotherm is represented as follows:

𝐶𝑒 𝐶𝑒 1
= + (9)
𝑞𝑒 Q𝑚𝑎𝑥 Q𝑚𝑎𝑥 x b

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Where qe (mgL-1) is the amount of Cd(II) adsorbed, Ce (mgL-1) is the equilibrium concentration

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for Cd(II). Qmax (mg g-1) is the maximum capacity of sorption per gram of sorbent and b is the

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Langmuir constant. When values of Ce/qe were plotted against Ce then a straight line with a high

correlation coefficient was obtained which confirms that Langmuir model provides the best fit of

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sorption as depicted in Fig. 8a. Values of Qmax and b were obtained from slope and intercept of
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straight lines, respectively (see Table 1). Maximum sorption capacity was calculated by

Langmuir isothermal model as 443.06 and 405.63 mg g-1 for DW and HGW, respectively. These
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values almost agree with experimental values of sorption capacity. The adsorption feasibility can
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be checked by applying the separation factor, RL, which is given by Eq. 10.
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1
𝑅𝐿 = (10)
1+ 𝐶𝑖
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The RL values between 0 and 1 favors the sorption and if the value of RL exceeds 1 then it

predicts unfavorable sorption. Here, the values of RL were calculated as 0.1714 and 0.1814 for
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DW and HGW, respectively (see Table 1). These values of RL between 0 and 1 shows a

favorable sorption of Cd(II) onto Na-OBMS sorbent.

The sorbent Na-OBMS is highly selective to Cd(II) over alkaline earth cations (Ca2+ and

Mg2+) and therefore less susceptible to interference from background ions, naturally present in

groundwater. Low sorption capacity for HGW as compared to DW can be attributed to the

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presence of alkaline earth metal cation (Ca2+ and Mg2+) naturally present in ground water which

compete with Cd(II) to reach the sorption sites. But this value of sorption capacity for HGW is

still higher as compared with some other polysaccharidal sorbents and it shows selectivity of the

sorbent for Cd(II) uptake in presence of Ca2+ and Mg2+. Hence, the sorption capacity of the

sorbent was not affected significantly by the ions naturally present in the studied groundwater.

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3.2.7. Kinetic modeling

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Data obtained from interaction time experiments was analyzed by pseudo-first order and pseudo-

second order kinetic model to establish the mechanism for sorption. Pseudo-first order kinetic

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model did not fit well whereas the pseudo-second order model provided the best fit. Pseudo-

second order kinetic model is given by Eq. 11.

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𝑡 1 𝑡
= + (11)
kqe2
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𝑞𝑡 𝑞𝑒

Where qe and qt are the quantity of metal sorbed at equilibrium and at time t, respectively and k
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(g mg-1 min-1) is the rate constant. A graph was plotted between t/qt and t which gives a straight
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line with high correlation coefficients (Fig. 8b). Slope and intercept of the straight line give value

of qe and k, respectively (see Table 1). Second order kinetic model provide greater values of R2
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as 0.9940 and 0.9947 for DW and HGW, respectively. The values of qe were obtained as 435.27
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mg g-1 and 397.96 mg g-1 for DW and HGW, respectively. All the data suggests almost an

agreement with experimental values and provide a better prediction of kinetic behavior by

second order kinetic model. This model also suggested that the removal of Cd(II) was carried out

by chemisorption.

3.2.8. Determination of thermodynamic parameters

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Data obtained from effect of temperature on metal ion uptake can be used to estimate different

thermodynamic parameters, i.e., Gibbs free energy (∆G°), entropy change (∆S°) and enthalpy

change (∆H°). The value of ∆S° and ∆H° can be obtained from slope and intercept of straight

line obtained by plotting lnK and 1/T (K-1) (Eq. 6, Fig. 8 c), respectively. Gibbs free energy was

calculated by Eq. 7. A spontaneous and exothermic behavior of sorption process suggested by

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the negative values of ∆G° and ∆H° whereas the negative value of ∆S° revealed a decline in

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randomness at the adsorbent to adsorbate interface when sorption takes place. All the necessary

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data regarding thermodynamic parameters is given in Table 1.

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0.50 0.4
DW HGW R² = 0.9911 DW HGW
0.45 0.35
0.40 0.3
Ce /qe (mg L-1/mg g-1)

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0.35

t/qt (min/mg g-1)

0.25
0.30
0.25 0.2
0.20 0.15
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0.15
0.1
0.10
0.05 0.05
a) b)
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0.00 0
0 50 100 150 200 0 20 40 60 80 100 120 140
Ce (mg L-1 ) t, min

3.5 DW HGW
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3
2.5
CE

2
1.5
ln Kc

1
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0.5
c)
0
0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034
1/T , K-1

Fig. 8. a) Fitting of Langmuir sorption isotherm model, b) Fitting of pseudo second order kinetic

model and c) Effect of temperature on sorption equilibrium constant for Cd(II) sorption from

DW and HGW.

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Table 1

Pseudo second order model, Langmuir isothermal model and thermodynamic parameters for
Cd(II) removal by using Na-OBMS sorbent.

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Models Parameters DW HGW

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Pseudo second order qe(mg g-1) 435.27 397.96
-1 -1

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k2(g mg min ) 0.0002 0.0002
R2 0.9940 0.9947

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Experimental qe(mg g-1) 395.0 360.0
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Langmuir parameters Qmax(mg g-1) 443.06 405.63
-1
b (mg L ) 0.0604 0.0564
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R2 0.9939 0.9911
RL 0.1714 0.1814
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Thermodynamic parameters ∆S°(J mol-1 K-1) -52.02 -15.64

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∆H°(kJ mol-1) -23.25 -8.963

2
R 0.9482 0.9870
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∆G°(kJ mol-1) -8.040 -4.298

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3.3 Recovery of sorbent by sorption-desorption

The sorbent was recovered for reuse under mild and green conditions by desorption of Cd(II)

ions by treating with brine. The regenerated sorbent was utilized in sorption studies for five

cycles. Decrease in sorption capacity was found to be 25 and 32 mg g-1 from DW and HGW,

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respectively (Fig. 9a and 9b) after five regeneration cycles. This method of recovery suggests

that repeated use of sorbent can be economically favorable.

Percentage metal uptake by OBMS was noted as 17% and 13% and by Na-OBMS as 96.5% and

93.5% for DW and HGW, respectively (Fig. 9c). This is strong evidence that sorption process

occurs through ion exchange mechanism. Since acidic form of the sorbent OBMS do not contain

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any ions to exchange with Cd(II) in solution so it shows less % uptake while it sodic form Na-

OBMS contains sodium ions to exchange with Cd(II) in solution so it shows high sorption

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capacity.

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360
400 Sorption Sorption
380 340
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Sorption capacity, mg g-1

Dsorption Desorption
Sorption capacity, mg g-1

360 320
340
300
320
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300 280
280 260
260
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240
240
220 220
1 2 3 4 5 1 2 3 4 5
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Number of cycles Number of cycles

CE
AC

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Fig. 9. Sorption and desorption of Cd(II) from (a)DW, (b) HGW and (c) percentage metal

uptake by OBMS and Na-OBMS. (sorption conditions: sorbent dosage = 20 mg/100 mL for both

DW and HGW, Cd(II) concentration = 80 mg L–1, temperature = 298 K, pH = 6.0 for both DW

and HGW solutions. Desorption conditions: 20 mg Cd(II)-loaded Na-OBMS/100 mL of

saturated solution of M NaCl contact time = 24 h at a temperature = 298 K)

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A comparison of previously polysaccharide sorbents with Na-OBMS shows that the current

sorbent might prove a super-sorbent for the removal of Cd(II) from HGW (Table 2). Literature

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showed that maiz straw [37], sugarcane [20], and mercerized cellulose [38] have been modified

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using succinic anhydride however the sorption capacities of these biomasses appeared low as

196.1, 196, and 86 mg g-1, respectively. Comparing to said similar nature and prominent works,
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sorbent (Na-OBMS) under present study showed relatively higher sorption capacities from DW

(443.06 mg g-1) and HGW (405.63 mg g-1).

M
ED

Table 2
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Comparison of Na-OBMS sorption capacity with other polysaccharide based reported sorbents
for Cd(II) uptake.
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Sorbent used Sorption capacity (mg g-1) Reference

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Maize straw (modified with 196.1 [37]

succinic anhydride) pH 4-7, 293 K.

Mercerized cellulose (succinic 86 [38]

anhydride)

Tamrix articulata waste (modified 195.5 [39]

by esterification with maleic acid)

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pH 4.0, 30o C, 2 h

Sugarcane bagasse (modified with 196 [20]

succinic anhydride)

H. verticillate plant seeds 37.46 [40]

(pH 7, 298 K, 2 h)

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Na-OBMS DW 443.06 Present

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HGW 405.63 work
(pH 6, 298 K)

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Present
work

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Values of sorption capacity of all sorbents are calculated using Langmuir model. Na-OBMS:
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sodium salt of OBMS; DW: deionized water; HGW: hard ground water.
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4. Conclusions
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Succinylated Ocimum basilicum mucilage after sodium salt formation was found as an efficient

sorbent material to remove Cd(II) from aqueous media. More than 93% Cd(II) metal removed
CE

within 20 min from both DW and HGW followed by ion exchange mechanism. Na-OBMS
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showed selective removal of Cd(II) uptake from HGW in spite of presence of bivalent cations

Ca+2 and Mg+2 which are present in ground water in higher amount. The current sorbent was

considered as an efficient and super-sorbent material due to the high sorption capacity (DW

443.06 and HGW 405.63 mg g-1) as compared to other polysaccharide based sorbents used for

Cd(II) uptake. Different thermodynamic parameters (with negative values) exhibited that the

sorption process is spontaneous and exothermic in nature. Fitting of sorption data to pseudo-

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second order and Langmuir models shows that chemisorption was responsible for Cd(II) uptake.

Sorbent was successfully recovered by treating with NaCl solution and reused for sorption to

remove Cd(II) over five cycles with a negligible decrease (9.5% for DW and 11.4% for HGW) in

their sorption capacity.

Acknowledgment

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We are thankful to Syed NA Bukhari, Jouf University, Aljouf, Saudi Arabia for the provision of

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solid state NMR spectroscopic analysis.

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Highlights

 Synthesis of Na-succinate bonded Ocimum basilicum mucilage (Na-OBMS)

 Characterization of sorbents

 Evaluation of Na-OBMS as a supersorbent for Cd(II) uptake

 Kinetic and isothermal modelling

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 Regeneration of sorbent Na-OBMS

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