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DOI: https://doi.org/10.1016/j.surfin.2018.12.004
Reference: SURFIN 269
Please cite this article as: Rasheed Ahmad Khera , Munawar Iqbal , Sobia Jabeen , Mazhar Abbas ,
Arif Nazir , Jan Nisar , Abdul Ghaffar , Ghulam Abbas Shar , M. Asif Tahir , Adsorption efficiency
of Pitpapra under single and binary metal systems, Surfaces and Interfaces (2018), doi:
https://doi.org/10.1016/j.surfin.2018.12.004
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Rasheed Ahmad Kheraa, Munawar Iqbal*,b, Sobia Jabeena, Mazhar Abbasc, Arif Nazirb, Jan
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Department of Chemistry, University of Agriculture, Faisalabad 38040, Pakistan
b
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Department of Chemistry, University of Lahore, Lahore, Pakistan
c
Jhang-Campus, University of Veterinary & Animal Sciences, Lahore, Pakistan
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d
National Centre of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120,
Pakistan
e
Department of Applied Chemistry and Biochemistry, Government College University,
Faisalabad, Pakistan
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Shah Abdul Latif University Khairpur- 66020, Sindh Pakistan
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*Corresponding author Email: bosalvee@yahoo.com
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Abstract
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In view of low cost and efficient adsorbents exploration, present study was aimed to evaluate the
possibility of Pitpapra waste biomass (roots, leaves, stem) for adsorption Zn (II) and Co (II)
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metals in single metal system (SMS) and binary metal system (BMS). The process variables
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were optimized for the maximum adsorption of metal ions. Pitpapra stem, leaves and root
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biomasses showed promising efficiency for the adsorption of Co (II) and Zn (II) ions and at
optimized conditions of process variable, 225 mg/g and 230 mg/g of Co (II) and Zn (II) ions
were removed from aqueous media. The behavior of Zn (II) in BMS changed, however, Co (II)
did not show any change in BMS versus SMS. Freundlich isotherm fitted well to the adsorption
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data of Co (II) and Zn (II). In view of efficient adsorption of Co (II) and Zn (II) ions, the use of
Pitpapra biomass is suggested for the adsorption of heavy metals from wastewater.
Keywords: Bio-sorption; Pitpapra waste biomass; heavy metals; single & binary system
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1. Introduction
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Pollution is a serious environmental and health issue. In spite of environmental regulations, the
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anthropogenic mixing of metal containing wastes in to water bodies has been increased to an
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alarming level [1-9]. Environmental pollution is a serious problem in industrialized countries as
metallic compounds used in industries, are discharged into the environment in excessive
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quantities [10-21]. These environmental effluents include heavy toxic metals such as lead (Pb),
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cobalt (Co), zinc (Zn), copper (Cu), nickel (Ni) and cadmium (Cd) are released from mining,
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chemical, dyes, paint, chemical and metal plating industries [22], which need to be treated before
being discharged into water bodies [1, 2, 23-25]. Metal ions not only affect plants and animals,
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but also enter food chain and are harmful for human beings [26]. Toxic heavy metals even in less
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concentration in environment are dangerous and produce extreme toxicity. Therefore, there is
need to develop treatment methods for the remediation of metals in effluents. Several
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conventional methods have been used for removal of heavy metal ions from wastewater i.e.,
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membrane filtration, adsorption [31] and bio-sorption [32, 33]. However, some methods are
expensive, more costly and less efficient [34] and other cause secondary pollution.
Bio-sorption is one of the promising [35] and commonly used techniques; however, commercial
adsorbent (based on costly source) makes the limited application of these adsorbents. So far, the
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biomass from plants, bacteria, fungi, algae [36, 37] should be investigated for the development of
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cost effective and efficient adsorbents for removal of metal ions from wastewater versus
commercial adsorbents [38]. The investigation using agricultural waste biomasses i.e., rice husk
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[39], bark of pine tree [40] and saw dust [41] revealed that plant based material are efficient
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adsorbent and able to remove metals completely. These bio-sorbents have diverse functional
groups and could be responsible for enhanced metal ion adsorption, also bio-sorption has many
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advantages such as easy handling, low cost adsorbent and recovery of useful metal ions [11, 19,
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42-45] over other conventional methods. Zn metal ions causes water pollution and leads to many
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health problems like gastrointestinal problem in human [46], Disharmony, pancreas damage,
arteriosclerosis and vertigo [47]. Co is discharged from alloy producing industries, electroplating
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and petroleum industries. It is harmful for living organisms brain and genetic diseases are also
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In view of toxic nature of Zn (II) and Co (II), Pitpapra (locally called Shahtrah) plant was used to
remove Zn (II) and Co (II) ions from aqueous solution as a function of pH, contact time, initial
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concentration of metal ions and temperature. Characterization of adsorbent was carried out by
FTIR technique. In view of multiple metals present in effluents, SMS and BMS were performed
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2.1. Chemicals and instruments
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The chemical used were of analytical grade i.e., HCl, NaOH, Co and Zn. AAS standards were
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purchased from Sigma-Aldrich. Ultra-pure water (Millipore system) was used for solution
preparation. Ultra-pure water with a resistivity of 18.2 MΩ cm from Milli-Q system (Millipore)
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was used for the preparation of solutions. The sieve (OCT-DIGITAL 4527-OI), analytical
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balance (Shimadzu, AW 220), orbital shaker incubator (PA 250/25.H), grinder (Moulinex,
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The herb Pitpapra was collected from village areas of Faisalabad, Pakistan. The plant was
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washed thoroughly with tap water to remove dust particles. Roots, stem and leaves were
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separated, dried in shade for a week followed by oven drying at 60 0C till constant weight. Dried
plant (root, stem and leaves) was grinded to fine powder and fraction of 0.25 mm and used for
adsorption of Zn (II) and Co (II). For preparation of stock solution of Co (II), 4.76 g of
CoSO4.7H2O was dissolved in 1L ultra-pure water. Working solutions were prepared by diluting
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stock solution of different concentrations. Zn (II) was prepared by dissolving 2.08 g of ZnCl2 in
1L ultra-pure water.
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For BMS, Co (II) concentration in the range of 25 to 150 mg/L and fixed concentration of 25 mL
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Zn (II) were used. The metal solution was mixed with respective amount of adsorbent and pH
solution was adjusted using 0.1M NaOH and HCl. For SMS system, 25 to 150 mg/L
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concentration was studied. The experiments were conducted in 250 mL flask at 120 rpm for 24 h.
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Mixture was filtered and Co (II) and Zn (II) residual concentration was analyzed and adsorption
par unit biomass and percentage adsorption was calculated using relations 1-2, respectively.
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Where, Ci and Ce are initial and final concentrations, V is volume and m is mass of adsorbent.
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( ) ( )
(1)
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CE
( ) (2)
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Where qe is adsorption capacity (mg/g), C0 is the initial concentration of dye (mg/L), C is the
concentration of dye at time t (mg/L), V is the volume of solution (mL) and m is the adsorbent
dose (g).
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Characterization of loaded and un-loaded biomass was carried out by FTIR (Fourier Transform
Infrared Spectroscopy) technique for the identification of functional groups involved in the
adsorption of Zn (II) and Co (II) ions. Pressed pellets were prepared by grinding the Pitpapra
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biomass with IR grade KBr in an agate mortar and subjected to FTIR analysis [50].
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3. Results and Discussion
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The Pitpapra possibilty was assessed for the removal of Co (II) and Zn (II) under SMS and BMS.
The effect of pH, contact time and Initial concentration of metal ions were srudied in detail.
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Effect of metal ion concentration is one of important parameters that potentially affect the
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adsorption of metal ions onto adsorbent. The effect of concentration on adsorption behavior has
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been shown in Fig. 1. The effect of concentration was studied in the range of 25 to 150 mg/L,
and at lower concentration of metal ions, the adsorption was low, which increased linearly which
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was due the availability of sorption sites, but the maximum adsorption was observed both Zn (II)
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and Co (II) up to 20-30 mg/L in SMS adsorption system and then, adsorption of both metals
became stable, which revealed that beyond this concentration, the sorption sites were exhausted
and no more adsorption was possible. In BMS, the adsorption behavior was different and
maximum adsorption was observed at higher concentration versus SMS. The Zn (II) and Co (II)
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metal ions adsorption in BMS enhanced up to 200 mg/L concentration in case of Zn (II), whereas
Co (II) adsorption did not change significantly in BMS versus SMS. The root, leave and stem of
Pitpapra plant showed different behavior for both metal ions adsorption. Concentration effect on
biosorption of Co (II) and Zn (II) showed that Co (II) ions adsorbed more efficiently as
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compared to Zn (II) ions in SMS, wheras in BMS, Zn (II) ions showed better sorption properties,
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which indicates that Zn (II) adsorpion is efficient versus Co (II). Previously, similar adsorption
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trends using different adsorbents as a function of metal ions initial concentration have been
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reported [51-63]. The enhanced dye adsorption at higher concentration was due to the driving
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forces to overcome mass transfer resistance of dye ions between the liquid and solid phases [64-
66]. At extremely higher initial concentration, the available binding sites were saturated and the
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adsorption depends on the initial concentration [14] and the probability of interaction of ions
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with binding sites becomes limited, which restricted the adsorption process. Therefore, for
effective adsorption, the ions in solution that interact with the binding sites are important that
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depends upon initial concentration. So, the adsorption sites were unsaturated initially and at
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higher concentration the competition between ions and available binding sites increased and
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hence, the complexation of ions was difficult, which reduced the adsorption slightly [64-
66]. Therefore, the concentration of both adsorbate and adsorbent are important, which must be
3.2. Effect of pH
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Metals have optimum range of pH in solution as well as their adsorption onto different adsorbent
is pH specific and at different pH values, the adsorption of metal ion may change significantly
[68]. The pH range of 3 to 9 (3, 4, 5, 6, 8, 9) was studied for Zn (II) and Co (II) metal ions
adsorption onto Pitpapra. At low pH, the adsorption was low, which was due to protonation and
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thus, surface of adsorbent became positive and uptake of Zn (II) and Co (II) ions was decreased,
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however, as the pH value increased, adsorption of metal ions also increased (Fig. 2). Thus, the
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different adsorption of metal ions may be explained on the basis of electrostatic
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interaction/repulsion between the adsorbent and ions. At lower pH, repulsive forces were
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dominant between the positively charged surface of adsorbent and metal cations. At higher pH,
the number of positively charged sites decreased and negatively charged sites became dominant.
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A negatively charged surface favors the adsorption of cations due to electrostatic attraction. [69,
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70]. Secondly, the functional groups are involved in the metal ions adsorption process and pH
affects the functional groups and resultantly, the forces between adsorbate and adsorbent may
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Optimization of contact time is also important parameter for economical wastewater treatment.
Fig. 3 shows the effect of contact time on adsorption of metals on Pitpapra biomass. The effect
of contact time on adsorption was studied in the range of 160 min, the adsorption of both metal
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ions increased linearly up to 145 min and then, became stable and no significant change was
observed for further contact time. The findings revealed that Pitpapra took consider longer time
to attain the equilibrium and previous studies also revealed that the native agricultural waste
biomasses attained equilibrium after longer contact time [10, 11, 14, 67, 71-73], which can be
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reduced by modification of native biomass [64, 65]. Overall, fast adsorption was observed
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initially followed by slower adsorption till equilibrium reached within 145 min. Further increase
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in contact time did not increase the adsorption and the lower adsorption rate at the latter stage
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may be due to the difficulty faced by ions to occupy the remaining vacant active sites and intra-
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particle diffusion process [64-67, 71]. This behavior of adsorption as function of contact time
may be explained as the sites were freely available to bind ions and in second phase, already
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exhausted sites may repel the coming ions as well as the concentration gradient between
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adsorbate and adsorbent also decreased with time [74, 75]. Similar finding have been
documented previously that with the passage of time the adsorption process may decreased due
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to difficulty faced by ions in occupying the few sites among most of the occupied sites [14, 64,
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Isotherm models are helpful in understanding the adsorption mechanism, which assume the
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assumes that adsorption occurs at specific homogeneous adsorption sites within the adsorbent
and intermolecular forces decrease rapidly with the distance from the adsorption surface [14, 67,
71]. The model further based on the assumption that all the adsorption sites are energetically
identical and adsorption occurs on a structurally similar binding site. The Langmuir adsorption
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isotherm is represented in Eq. 3 and linear form of this isotherm is expressed in Eq. 4.
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(3)
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(4)
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Where, qmax (mg/g) is maximum adsorption capacity and b (L/mg) is Langmuir constants
Freundlich isotherm model can be used to describe the sorption on heterogeneous surfaces as
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well as a multilayer sorption. It assumes that the uptake of adsorbate ion occurs on a
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heterogeneous adsorbent surface. The Freundlich isotherm model is empirical in nature which
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assumes that the stronger binding sites are occupied first and that the binding strength decreases
with increasing degree of site occupation. The non-linear and linear forms of Freundlich
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(5)
(6)
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Where, KF and n are the Freundlich model constants designated as adsorption capacity and
adsorption intensity respectively, which can be obtained from slope and intercept of the plot of
logqe versus logCe. Ce is the residual concentration of solute in solution (mg/L), qe is the amount
of adsorbate adsorbed by a unit mass of adsorbent at equilibrium (mg/g). The curves obtained in
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case of Co (II) adsorption (log Ce versus log qe) are shown in Fig. 4 for Langmuir isotherm,
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whereas Freundlich model responses are shown in Fig. 5. Langmuir isotherm did not show linear
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trend both for Co (II) and Zn (II) ions. Moreover, R2 values are also low. Freundlich isotherm
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showed linear response for the adsorption of Co (II) and Zn (II) ions. R2 values for stem, leaves
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and root biomasses were 0.9483, 0.8069 and 0.926 in case of Co (II) ions, respectively, which
are acceptable. Similarly, Zn (II) ions adsorption on to leaves, stem and roots also showed larger
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regression coefficient values, which indicates that both Zn (II) and Co (II) followed Freundlich
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isotherm. The Freundlich isotherm model described the adsorption on heterogeneous surface,
which is not restricted to the formation of monolayer. The values of R2 in case of Freundlich
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isotherm model were greater than those obtained for Langmuir model and also qe values were
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close to experimentally determined values, which indicate that the Freundlich isotherm model
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FTIR analysis was carried out for characterization of adsorbent before and after adsorption of
metal ions to identify functional groups responsible for adsorption of Zn (II) and Co (II) ions.
The peak at 3300 cm-1 is assigned to hydroxyl group, 2900 cm-1 and 2850 cm-1 revealed CH2 and
CH3 groups respectively (Fig. 6). The peaks at 1600 cm-1 and 1400 cm-1 indicated the presence
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of carbonyl and ionic carboxylic groups respectively. FTIR spectra of loaded biomass indicated
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that intensity of peak of hydroxyl group was decreased and an additional sharp peak at 900 cm-1
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showed C-OH stretching vibration and carbonyl peak is obtained at 1720 cm-1, which indicates
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that hydroxyl, carbonyl and ionic carboxylic groups involved in the adsorption of Zn (II) and Co
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(II) ions. Overall, results revealed that Pitpapra biomass has potential for the adsorption of metal
ions and could possibly be used for environmental remediation [6, 77-97].
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4. Conclusions
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The Zn (II) and Co (II) ions adsorption using Pitpapra biomass was investigated. Under
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optimized conditions, 225 mg/g and 230 mg/g of Co (II) and Zn (II) ions were adsorbed onto
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Pitpapra biomass. The behavior of Co (II) and Zn (II) ions adsorption was changed significantly
in SMS and BMS. Both ions followed Freundlich isotherm as compared to Langmuir isotherm
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for Zn (II) and Co (II) metal ions. In view of efficient adsorption of Co (II) and Zn (II) ions, the
Pitpapra biomass could possibly be used for the adsorption of heavy metals from wastewater and
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Fig. 1: (A-F) Single metal adsorption system (A) Effect of metal ion concentration on adsorption of Zn
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(II) and Co (II) ions onto Pitpapra leave biomass, (B) Effect of metal ion concentration on adsorption of
Zn (II) and Co (II) ions onto Pitpapra stem biomass, (C) Effect of metal ion concentration on adsorption
of Zn (II) and Co (II) ions onto Pitpapra root biomass and (D-F) binary metal adsorption system (D)
Effect of metal ion concentration on adsorption of Zn (II) and Co (II) ions onto Pitpapra leave biomass
(E) Effect of metal ion concentration on adsorption of Zn (II) and Co (II) ions onto Pitpapra stem biomass
(F) Effect of metal ion concentration on adsorption of Zn (II) and Co (II) ions onto Pitpapra root biomass
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Fig. 2: Effect of pH on adsorption of Zn (II) and Co (II) ions onto Pitpapra (A) leave , (B) stem
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Fig. 3: Effect of contact time on adsorption of Zn (II) and Co (II) ions onto Pitpapra biomasses
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0.03
0.025
(A)
0.02
Ce/qe
0.015
0.01
y = 1E-05x + 0.0147
0.005 R² = 0.0007
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Ce (mg/L)
0.02
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(B)
0.015
Ce/qe
0.005
0.01
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R² = 0.6569
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0 10 20 30 40
Ce (mg/L)
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(C)
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Ce (mg/L)
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0.008
(D)
0.006
Ce/qe
0.004
y = 0.0003x + 0.0023
0.002 R² = 0.9971
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Ce (mg/L)
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0.025
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(E)
0.015
Ce/qe
0.01
0.005
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R² = 0.9655
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(F)
0.01
Ce/qe
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Fig. 4: Langmuir isotherm (A) Co (II) adsorption onto leave (B) Co (II) adsorption onto stem,
(C) Co (II) adsorption onto root, (D) Zn (II) adsorption onto leave, (E) Zn (II) adsorption onto
stem and (F) Zn (II) adsorption onto root
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(A)
log qe (mg/g)
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1 y = 0.9003x + 1.9665
R² = 0.8069
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0 0.5 1 1.5 2
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(B)
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log qe (mg/g)
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y = 0.8079x + 2.1753
R² = 0.9483
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log Ce (mg/L)
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(C)
log qe (mg/g)
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y = 1.0715x + 1.5682
R² = 0.926
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(D)
log qe (mg/g)
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1 y = 0.6018x + 2.653
R² = 0.969
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(E)
log qe (mg/g)
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R² = 0.9355
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log Ce (mg/L)
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(F)
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log qe (mg/g)
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y = 0.8234x + 2.2436
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1 R² = 0.9688
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log Ce (mg/L)
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Fig. 5: Freundlich isotherm (A) Co (II) adsorption on to leaves, (B) Co (II) adsorption on to
stem, (C) Co (II) adsorption on to root, (A) Zn (II) adsorption on to leaves, (B) Zn (II) adsorption
on to stem, (C) Zn (II) adsorption on to root
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Fig. 6: FTIR spectra (A) leave biomass before adsorption, (B) leaves biomass after adsorption,
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(C) stem biomass before adsorption and (D) stem biomass after adsorption
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