Sie sind auf Seite 1von 27

Accepted Manuscript

Adsorption efficiency of Pitpapra under single and binary metal


systems

Rasheed Ahmad Khera , Munawar Iqbal , Sobia Jabeen ,


Mazhar Abbas , Arif Nazir , Jan Nisar , Abdul Ghaffar ,
Ghulam Abbas Shar , M. Asif Tahir

PII: S2468-0230(18)30557-1
DOI: https://doi.org/10.1016/j.surfin.2018.12.004
Reference: SURFIN 269

To appear in: Surfaces and Interfaces

Received date: 22 October 2016


Revised date: 31 December 2017
Accepted date: 4 December 2018

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

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service
to our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and
all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT

Adsorption efficiency of Pitpapra under single and binary metal systems

Rasheed Ahmad Kheraa, Munawar Iqbal*,b, Sobia Jabeena, Mazhar Abbasc, Arif Nazirb, Jan

Nisard, Abdul Ghaffare, Ghulam Abbas Sharf and M. Asif Tahira

T
Department of Chemistry, University of Agriculture, Faisalabad 38040, Pakistan
b

IP
Department of Chemistry, University of Lahore, Lahore, Pakistan
c
Jhang-Campus, University of Veterinary & Animal Sciences, Lahore, Pakistan

CR
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
f US
Shah Abdul Latif University Khairpur- 66020, Sindh Pakistan
AN
*Corresponding author Email: bosalvee@yahoo.com
M

Abstract
ED

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)
PT

metals in single metal system (SMS) and binary metal system (BMS). The process variables
CE

were optimized for the maximum adsorption of metal ions. Pitpapra stem, leaves and root
AC

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

1
ACCEPTED MANUSCRIPT

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

T
1. Introduction

IP
Pollution is a serious environmental and health issue. In spite of environmental regulations, the

CR
anthropogenic mixing of metal containing wastes in to water bodies has been increased to an

US
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
AN
quantities [10-21]. These environmental effluents include heavy toxic metals such as lead (Pb),
M

cobalt (Co), zinc (Zn), copper (Cu), nickel (Ni) and cadmium (Cd) are released from mining,
ED

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,
PT

but also enter food chain and are harmful for human beings [26]. Toxic heavy metals even in less
CE

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
AC

conventional methods have been used for removal of heavy metal ions from wastewater i.e.,

extraction [27], ion exchange [28] , electroplating, filtration, oxidation, phytoremediation,

reduction, evaporation [29], precipitation [30] coagulation, electro-dialysis , reverse osmosis,

2
ACCEPTED MANUSCRIPT

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

T
IP
biomass from plants, bacteria, fungi, algae [36, 37] should be investigated for the development of

CR
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

US
[39], bark of pine tree [40] and saw dust [41] revealed that plant based material are efficient
AN
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
M

advantages such as easy handling, low cost adsorbent and recovery of useful metal ions [11, 19,
ED

42-45] over other conventional methods. Zn metal ions causes water pollution and leads to many
PT

health problems like gastrointestinal problem in human [46], Disharmony, pancreas damage,

arteriosclerosis and vertigo [47]. Co is discharged from alloy producing industries, electroplating
CE

and petroleum industries. It is harmful for living organisms brain and genetic diseases are also
AC

caused due to Co toxicity, which may lead to cancer [48, 49].

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

3
ACCEPTED MANUSCRIPT

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

to evaluate the efficiency of Pitpapra biomass.

2. Materials and Methods

T
IP
2.1. Chemicals and instruments

CR
The chemical used were of analytical grade i.e., HCl, NaOH, Co and Zn. AAS standards were

US
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)
AN
was used for the preparation of solutions. The sieve (OCT-DIGITAL 4527-OI), analytical
M

balance (Shimadzu, AW 220), orbital shaker incubator (PA 250/25.H), grinder (Moulinex,
ED

France), pH meter (HI-8014 Hanna), and AAS (AA-6200) (otherwise stated).

2.2. Biomass collection and preparation


PT

The herb Pitpapra was collected from village areas of Faisalabad, Pakistan. The plant was
CE

washed thoroughly with tap water to remove dust particles. Roots, stem and leaves were
AC

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

4
ACCEPTED MANUSCRIPT

stock solution of different concentrations. Zn (II) was prepared by dissolving 2.08 g of ZnCl2 in

1L ultra-pure water.

2.4. Batch Bio-sorption studies of SMS and BMS

T
IP
For BMS, Co (II) concentration in the range of 25 to 150 mg/L and fixed concentration of 25 mL

CR
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

US
concentration was studied. The experiments were conducted in 250 mL flask at 120 rpm for 24 h.
AN
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.
M

Where, Ci and Ce are initial and final concentrations, V is volume and m is mass of adsorbent.
ED

( ) ( )
(1)
PT
CE

( ) (2)
AC

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).

5
ACCEPTED MANUSCRIPT

2.6. FTIR analysis

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

T
IP
biomass with IR grade KBr in an agate mortar and subjected to FTIR analysis [50].

CR
3. Results and Discussion

US
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.
AN

3.1. Effect of metal ion concentration


M

Effect of metal ion concentration is one of important parameters that potentially affect the
ED

adsorption of metal ions onto adsorbent. The effect of concentration on adsorption behavior has
PT

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
CE

was due the availability of sorption sites, but the maximum adsorption was observed both Zn (II)
AC

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)

6
ACCEPTED MANUSCRIPT

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

T
compared to Zn (II) ions in SMS, wheras in BMS, Zn (II) ions showed better sorption properties,

IP
which indicates that Zn (II) adsorpion is efficient versus Co (II). Previously, similar adsorption

CR
trends using different adsorbents as a function of metal ions initial concentration have been

US
reported [51-63]. The enhanced dye adsorption at higher concentration was due to the driving
AN
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
M

adsorption depends on the initial concentration [14] and the probability of interaction of ions
ED

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
PT

depends upon initial concentration. So, the adsorption sites were unsaturated initially and at
CE

higher concentration the competition between ions and available binding sites increased and
AC

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

in equilibrium for effective adsorption [67].

3.2. Effect of pH

7
ACCEPTED MANUSCRIPT

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

T
thus, surface of adsorbent became positive and uptake of Zn (II) and Co (II) ions was decreased,

IP
however, as the pH value increased, adsorption of metal ions also increased (Fig. 2). Thus, the

CR
different adsorption of metal ions may be explained on the basis of electrostatic

US
interaction/repulsion between the adsorbent and ions. At lower pH, repulsive forces were
AN
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.
M

A negatively charged surface favors the adsorption of cations due to electrostatic attraction. [69,
ED

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
PT

change [67, 71].


CE

3.3. Effect of contact time on Zn (II)


AC

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

8
ACCEPTED MANUSCRIPT

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

T
reduced by modification of native biomass [64, 65]. Overall, fast adsorption was observed

IP
initially followed by slower adsorption till equilibrium reached within 145 min. Further increase

CR
in contact time did not increase the adsorption and the lower adsorption rate at the latter stage

US
may be due to the difficulty faced by ions to occupy the remaining vacant active sites and intra-
AN
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
M

exhausted sites may repel the coming ions as well as the concentration gradient between
ED

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
PT

to difficulty faced by ions in occupying the few sites among most of the occupied sites [14, 64,
CE

65, 67, 74, 76].


AC

3.4. Equilibrium Modeling

Isotherm models are helpful in understanding the adsorption mechanism, which assume the

adsorption of adsorbate as a function of equilibrium concentration. Langmuir adsorption model

9
ACCEPTED MANUSCRIPT

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

T
isotherm is represented in Eq. 3 and linear form of this isotherm is expressed in Eq. 4.

IP
CR
(3)

US
(4)
AN
Where, qmax (mg/g) is maximum adsorption capacity and b (L/mg) is Langmuir constants

related to the heat of adsorption.


M

Freundlich isotherm model can be used to describe the sorption on heterogeneous surfaces as
ED

well as a multilayer sorption. It assumes that the uptake of adsorbate ion occurs on a
PT

heterogeneous adsorbent surface. The Freundlich isotherm model is empirical in nature which
CE

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
AC

isotherm model are shown in Eq. 5 and 6, respectively.

(5)

(6)

10
ACCEPTED MANUSCRIPT

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

T
case of Co (II) adsorption (log Ce versus log qe) are shown in Fig. 4 for Langmuir isotherm,

IP
whereas Freundlich model responses are shown in Fig. 5. Langmuir isotherm did not show linear

CR
trend both for Co (II) and Zn (II) ions. Moreover, R2 values are also low. Freundlich isotherm

US
showed linear response for the adsorption of Co (II) and Zn (II) ions. R2 values for stem, leaves
AN
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
M

regression coefficient values, which indicates that both Zn (II) and Co (II) followed Freundlich
ED

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
PT

isotherm model were greater than those obtained for Langmuir model and also qe values were
CE

close to experimentally determined values, which indicate that the Freundlich isotherm model
AC

explained metal ions adsorption well.

3.5. FTIR Analysis

11
ACCEPTED MANUSCRIPT

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

T
of carbonyl and ionic carboxylic groups respectively. FTIR spectra of loaded biomass indicated

IP
that intensity of peak of hydroxyl group was decreased and an additional sharp peak at 900 cm-1

CR
showed C-OH stretching vibration and carbonyl peak is obtained at 1720 cm-1, which indicates

US
that hydroxyl, carbonyl and ionic carboxylic groups involved in the adsorption of Zn (II) and Co
AN
(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].
M

4. Conclusions
ED

The Zn (II) and Co (II) ions adsorption using Pitpapra biomass was investigated. Under
PT

optimized conditions, 225 mg/g and 230 mg/g of Co (II) and Zn (II) ions were adsorbed onto
CE

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
AC

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

modified biomass might be more efficient versus native biomass.

12
ACCEPTED MANUSCRIPT

References

[1] K. Thirumalai, E.T.D. Kumar, R. Aravindhan, J.R. Rao, M. Swaminathan, Hierarchically structured
bentonite loaded Bi2O3-ZnO and its multiple applications, Surf. Interfaces. 5 (2016) 30-38.
[2] H. Tounsadi, A. Khalidi, M. Farnane, A. Machrouhi, A. Elhalil, N. Barka, Adsorptive removal of heavy

T
metals from aqueous solution using chemically activated Diplotaxis Harra biomass, Surf. Interfaces. 4
(2016) 84-94.

IP
[3] N.K. Benabdallah, D. Harrache, A. Mir, M. de la Guardia, F.-Z. Benhachem, Bioaccumulation of trace
metals by red alga Corallina elongata in the coast of Beni Saf, west coast, Algeria, Chem. Int. 3 (2017)

CR
220-231.
[4] A.M. Engida, B.S. Chandravanshi, Assessment of heavy metals in tobacco of cigarettes commonly sold
in Ethiopia, Chem. Int. 3 (2017) 213-219.
[5] S. Fait, S. Fakhi, M. ElMzibri, Z. Faiz, H. Fougrach, W. Badri, A. Smouni, M. Fahr, Distribution of

Chem. Int. 3 (2017) 278-285. US


metallic trace elements (ETM) in surface soils around the mediouna discharge (southern of Casablanca),

[6] A. Sasmaz, I.M. Dogan, M. Sasmaz, Removal of Cr, Ni and Co in the water of chromium mining areas
AN
by using Lemna gibba L. and Lemna minor L, Water Environ. J. 30 (2016) 235-242.
[7] M. Sasmaz, B. Akgül, D. Yıldırım, A. Sasmaz, Mercury uptake and phytotoxicity in terrestrial plants
grown naturally in the Gumuskoy (Kutahya) mining area, Turkey, Int. J. Phytoremediat. 18 (2016) 69-76.
[8] M. Sasmaz, E. Obek, A. Sasmaz, Bioaccumulation of Uranium and Thorium by Lemna minor and
M

Lemna gibba in Pb-Zn-Ag Tailing Water, Bull. Environ. Contam. Toxicol. 97 (2016) 832-837.
[9] M. Sasmaz, E.I.A. Topal, E. Obek, A. Sasmaz, The potential of Lemna gibba L. and Lemna minor L. to
remove Cu, Pb, Zn, and As in gallery water in a mining area in Keban, Turkey, J. Environ. manage. 163
(2015) 246-253.
ED

[10] M. Iqbal, R.A. Khera, Adsorption of copper and lead in single and binary metal system onto Fumaria
indica biomass, Chem. Int. 1 (2015) 157b-163b.
[11] A. Babarinde, G.O. Onyiaocha, Equilibrium sorption of divalent metal ions onto groundnut (Arachis
PT

hypogaea) shell: kinetics, isotherm and thermodynamics, Chem. Int. 2 (2016) 37-46.
[12] B.K. Pandey, S. Vyas, M. Pandey, A. Gaur, Characterisation of municipal solid waste generated from
Bhopal, India, Curr. Sci. Perspect. 2 (2016) 52-56.
[13] M.A. Jamal, M. Muneer, M. Iqbal, Photo-degradation of monoazo dye blue 13 using advanced
CE

oxidation process, Chem. Int. 1 (2015) 12-16.


[14] Q. Manzoor, R. Nadeem, M. Iqbal, R. Saeed, T.M. Ansari, Organic acids pretreatment effect on Rosa
bourbonia phyto-biomass for removal of Pb (II) and Cu (II) from aqueous media, Bioresource Technol.
AC

132 (2013) 446-452.


[15] T. Onishi, S.-i. Koyama, H. Mimura, Removal of zirconium from spent fuel solution by alginate gel
polymer, Prog. Nuc. Energ. 82 (2015) 69-73.
[16] M.H. Sayadi, M. Shabani, N. Ahmadpour, Pollution Index and Ecological Risk of Heavy Metals in the
Surface Soils of Amir-Abad Area in Birjand City, Iran, (2015).
[17] M. Sayed, Efficient removal of phenol from aqueous solution by the pulsed high-voltage discharge
process in the presence of H2O2, Chem. Int. 1 (2015) 81-86.

13
ACCEPTED MANUSCRIPT

[18] A. Babarinde, K. Ogundipe, K.T. Sangosanya, B.D. Akintola, A.-O. Elizabeth Hassan, Comparative
study on the biosorption of Pb(II), Cd(II) and Zn(II) using Lemon grass (Cymbopogon citratus): kinetics,
isotherms and thermodynamics, Chem. Int. 2 (2016) 89-102.
[19] S. Jafarinejad, Control and treatment of sulfur compounds specially sulfur oxides (SOx) emissions
from the petroleum industry: a review, Chem. Int. 2 (2016) 242-253.
[20] S. Jafarinejad, Recent developments in the application of sequencing batch reactor (SBR)
technology for the petroleum industry wastewater treatment, Chem. Int. 3(3) (2017) 241-250.
[21] S. Jafarinejad, Activated sludge combined with powdered activated carbon (PACT process) for the
petroleum industry wastewater treatment: A review, Chem. Int. 3 (2017) 268-277.

T
[22] M. Riaz, R. Nadeem, M.A. Hanif, T.M. Ansari, Pb (II) biosorption from hazardous aqueous streams
using Gossypium hirsutum (Cotton) waste biomass, J. Hazard. Mater. 161 (2009) 88-94.

IP
[23] C. Ukpaka, BTX Degradation: The concept of microbial integration, Chem Int, 3 (2016) 8-18.
[24] C. Ukpaka, S.N.-A. Adaobi, C. Ukpaka, Development and evaluation of trans-amadi groundwater

CR
parameters: The integration of finite element techniques, Chem. Int. 3 (2017) 306-317.
[25] C. Ukpaka, T. Izonowei, Model Prediction on the Reliability of Fixed Bed Reactor for Ammonia
Production, Chem. Int. 3 (2017) 46-57.
[26] J. Nouri, B. Lorestani, N. Yousefi, N. Khorasani, A. Hasani, F. Seif, M. Cheraghi, Phytoremediation

Earth Sci. 62 (2011) 639-644.


US
potential of native plants grown in the vicinity of Ahangaran lead–zinc mine (Hamedan, Iran), Environ.

[27] J.R. Kumar, H.-I. Lee, J.-Y. Lee, J.-S. Kim, J.-S. Sohn, Comparison of liquid–liquid extraction studies on
platinum (IV) from acidic solutions using bis (2, 4, 4-trimethylpentyl) monothiophosphinic acid, Sep.
AN
Purif. Technol. 63 (2008) 184-190.
[28] E. Els, L. Lorenzen, C. Aldrich, The adsorption of precious metals and base metals on a quaternary
ammonium group ion exchange resin, Miner. Eng. 13 (2000) 401-414.
[29] C.S. Brooks, P.L. Brooks, G. Hansen, L.A. MacCarthy, Metal recovery from industrial waste, Lewis
M

Publishers Chelsea, MI1991.


[30] M. McDonald, I. Mila, A. Scalbert, Precipitation of metal ions by plant polyphenols: optimal
conditions and origin of precipitation, J. Agric. Food Chem. 44 (1996) 599-606.
ED

[31] A. Uheida, M. Iglesias, C. Fontàs, M. Hidalgo, V. Salvadó, Y. Zhang, M. Muhammed, Sorption of


palladium (II), rhodium (III), and platinum (IV) on Fe3O4 nanoparticles, J. Colloid Interface Sci. 301 (2006)
402-408.
[32] I. Anastopoulos, G.Z. Kyzas, Composts as biosorbents for decontamination of various pollutants: a
PT

review, Water Air Soil Poll. 226 (2015) 1-16.


[33] M.A. Javed, H.N. Bhatti, M.A. Hanif, R. Nadeem, Kinetic and equilibrium modeling of Pb (II) and Co
(II) sorption onto rose waste biomass, Sep. Sci. Technol. 42 (2007) 3641-3656.
CE

[34] R. Ayyappan, A.C. Sophia, K. Swaminathan, S. Sandhya, Removal of Pb (II) from aqueous solution
using carbon derived from agricultural wastes, Proc. Biochem. 40 (2005) 1293-1299.
[35] K. Vijayaraghavan, Biosorption of metals: a complete handbook, Vinanie Publishers, Chennai, India,
2016.
AC

[36] K. Deepa, M. Sathishkumar, A. Binupriya, G. Murugesan, K. Swaminathan, S. Yun, Sorption of Cr (VI)


from dilute solutions and wastewater by live and pretreated biomass of Aspergillus flavus,
Chemosphere. 62 (2006) 833-840.
[37] A. Özer, G. Gürbüz, A. Çalimli, B.K. Körbahti, Biosorption of copper (II) ions on Enteromorpha
prolifera: application of response surface methodology (RSM), Chem. Eng. J. 146 (2009) 377-387.
[38] M. Bilal, J.A. Shah, T. Ashfaq, S.M.H. Gardazi, A.A. Tahir, A. Pervez, H. Haroon, Q. Mahmood, Waste
biomass adsorbents for copper removal from industrial wastewater—A review, J. Hazard. Mater. 263
(2013) 322-333.

14
ACCEPTED MANUSCRIPT

[39] A. Kausar, H.N. Bhatti, G. MacKinnon, Equilibrium, kinetic and thermodynamic studies on the
removal of U (VI) by low cost agricultural waste, Colloid. Surface-B 111 (2013) 124-133.
[40] A. Gundogdu, D. Ozdes, C. Duran, V.N. Bulut, M. Soylak, H.B. Senturk, Biosorption of Pb (II) ions
from aqueous solution by pine bark (Pinus brutia Ten.), Chem. Eng. J. 153 (2009) 62-69.
[41] A.E. Ofomaja, Intraparticle diffusion process for lead (II) biosorption onto mansonia wood sawdust,
Bioresource Technol. 101 (2010) 5868-5876.
[42] C. Quintelas, V.B. da Silva, B. Silva, H. Figueiredo, T. Tavares, Optimization of production of
extracellular polymeric substances by Arthrobacter viscosus and their interaction with a 13X zeolite for
the biosorption of Cr (VI), Environ. Technol. 32 (2011) 1541-1549.

T
[43] R.M. Ali, H.A. Hamad, M.M. Hussein, G.F. Malash, Potential of using green adsorbent of heavy metal
removal from aqueous solutions: Adsorption kinetics, isotherm, thermodynamic, mechanism and

IP
economic analysis, Ecol. Eng. 91 (2016) 317-332.
[44] A. Banerjee, P. Sarkar, S. Banerjee, Application of statistical design of experiments for optimization

CR
of As (V) biosorption by immobilized bacterial biomass, Ecol. Eng. 86 (2016) 13-23.
[45] M.L. Paul, J. Samuel, N. Chandrasekaran, A. Mukherjee, Comparative kinetics, equilibrium,
thermodynamic and mechanistic studies on biosorption of hexavalent chromium by live and heat killed
biomass of Acinetobacter junii VITSUKMW2, an indigenous chromite mine isolate, Chem. Eng. J. 187
(2012) 104-113.
US
[46] S. Tunali, T. Akar, Zn (II) biosorption properties of Botrytis cinerea biomass, J. Hazard. Mater. 131
(2006) 137-145.
[47] T. Depci, A.R. Kul, Y. Önal, Competitive adsorption of lead and zinc from aqueous solution on
AN
activated carbon prepared from Van apple pulp: Study in single-and multi-solute systems, Chem. Eng. J.
200 (2012) 224-236.
[48] N. Kuyucak, B. Volesky, Accumulation of cobalt by marine alga, Biotechnol. Bioeng. 33 (1989) 809-
814.
M

[49] M. Nordberg, G.F. Nordberg, Trace element research-historical and future aspects, J. Trace Elem.
Med. Bio. 38 (2016) 46-52.
[50] A. Ashar, M. Iqbal, I.A. Bhatti, M.Z. Ahmad, K. Qureshi, J. Nisar, I.H. Bukhari, Synthesis,
ED

characterization and photocatalytic activity of ZnO flower and pseudo-sphere: Nonylphenol ethoxylate
degradation under UV and solar irradiation, J. Alloy Comp. 678 (2016) 126-136.
[51] H.-Y. Zhu, Y.-Q. Fu, R. Jiang, J. Yao, L. Xiao, G.-M. Zeng, Novel magnetic chitosan/poly (vinyl alcohol)
hydrogel beads: Preparation, characterization and application for adsorption of dye from aqueous
PT

solution, Bioresource Technol. 105 (2012) 24-30.


[52] H. Yan, H. Li, H. Yang, A. Li, R. Cheng, Removal of various cationic dyes from aqueous solutions using
a kind of fully biodegradable magnetic composite microsphere, Chem. Eng. J. 223 (2013) 402-411.
CE

[53] H.-Y. Zhu, R. Jiang, L. Xiao, W. Li, A novel magnetically separable γ-Fe2O3/crosslinked chitosan
adsorbent: preparation, characterization and adsorption application for removal of hazardous azo dye, J.
Hazard. Mater. 179 (2010) 251-257.
[54] I. Safarik, K. Horska, B. Svobodova, M. Safarikova, Magnetically modified spent coffee grounds for
AC

dyes removal, Eur. Food Res. Technol. 234 (2012) 345-350.


[55] I. Safarik, M. Safarikova, Magnetic fluid modified peanut husks as an adsorbent for organic dyes
removal, Phys. Proced. 9 (2010) 274-278.
[56] P.R. Chang, P. Zheng, B. Liu, D.P. Anderson, J. Yu, X. Ma, Characterization of magnetic soluble
starch-functionalized carbon nanotubes and its application for the adsorption of the dyes, J. Hazard.
Mater. 186 (2011) 2144-2150.
[57] F. Ge, H. Ye, M.-M. Li, B.-X. Zhao, Efficient removal of cationic dyes from aqueous solution by
polymer-modified magnetic nanoparticles, Chem. Eng. J. 198 (2012) 11-17.

15
ACCEPTED MANUSCRIPT

[58] S. Wang, Y.-Y. Zhai, Q. Gao, W.-J. Luo, H. Xia, C.-G. Zhou, Highly efficient removal of acid red 18 from
aqueous solution by magnetically retrievable chitosan/carbon nanotube: batch study, isotherms,
kinetics, and thermodynamics, J. Chem. Eng. Data. 59 (2013) 39-51.
[59] L. Zhou, J. Jin, Z. Liu, X. Liang, C. Shang, Adsorption of acid dyes from aqueous solutions by the
ethylenediamine-modified magnetic chitosan nanoparticles, J. Hazard. Mater. 185 (2011) 1045-1052.
[60] A. Debrassi, T. Baccarin, C.A. Demarchi, N. Nedelko, A. Ślawska-Waniewska, P. Dłużewski, M. Bilska,
C.A. Rodrigues, Adsorption of Remazol Red 198 onto magnetic N-lauryl chitosan particles: equilibrium,
kinetics, reuse and factorial design, Environ. Sci. Poll. Res. 19 (2012) 1594-1604.
[61] D. Fungaro, M. Yamaura, T. Carvalho, Adsorption of anionic dyes from aqueous solution on О zeolite

T
from fly ash-iron oxide magnetic-nanocomposite, J. At. Mol. Sci.2 (2011) 305-316.
[62] D.-P. Li, Y.-R. Zhang, X.-X. Zhao, B.-X. Zhao, Magnetic nanoparticles coated by aminoguanidine for

IP
selective adsorption of acid dyes from aqueous solution, Chem. Eng. J. 232 (2013) 425-433.
[63] N.M. Mahmoodi, Magnetic ferrite nanoparticle–alginate composite: Synthesis, characterization and

CR
binary system dye removal, J. Taiwan Inst. Chem. E. 44 (2013) 322-330.
[64] M. Mushtaq, H.N. Bhatti, M. Iqbal, S. Noreen, Eriobotrya japonica seed biocomposite efficiency for
copper adsorption: Isotherms, kinetics, thermodynamic and desorption studies, J. Environ. Manage.
(2016).

US
[65] A. Rashid, H.N. Bhatti, M. Iqbal, S. Noreen, Fungal biomass composite with bentonite efficiency for
nickel and zinc adsorption: a mechanistic study, Ecol. Eng. 91 (2016) 459-471.
[66] M.A. Tahir, H.N. Bhatti, M. Iqbal, Solar Red and Brittle Blue direct dyes adsorption onto Eucalyptus
angophoroides bark: Equilibrium, kinetics and thermodynamic studies, J. Environ. Chem. Eng. 4 (2016)
AN
2431-2439.
[67] I. Ullah, R. Nadeem, M. Iqbal, Q. Manzoor, Biosorption of chromium onto native and immobilized
sugarcane bagasse waste biomass, Ecol. Eng. 60 (2013) 99-107.
[68] F. Pagnanelli, A. Esposito, L. Toro, F. Veglio, Metal speciation and pH effect on Pb, Cu, Zn and Cd
M

biosorption onto Sphaerotilus natans: Langmuir-type empirical model, Water Res. 37 (2003) 627-633.
[69] J. Wang, Q. Zhou, D. Song, B. Qi, Y. Zhang, Y. Shao, Z. Shao, Chitosan–silica composite aerogels:
preparation, characterization and Congo red adsorption, J. Sol-Gel Sci. Technol. 76 (2015) 501-509.
ED

[70] L. Wang, A. Wang, Adsorption characteristics of Congo Red onto the chitosan/montmorillonite
nanocomposite, J. Hazard. Mater. 147 (2007) 979-985.
[71] R. Nadeem, Q. Manzoor, M. Iqbal, J. Nisar, Biosorption of Pb (II) onto immobilized and native
Mangifera indica waste biomass, J. Indus. Eng. Chem. 35 (2016) 184-195.
PT

[72] Z. Aksu, I.A. Isoglu, Use of agricultural waste sugar beet pulp for the removal of Gemazol turquoise
blue-G reactive dye from aqueous solution, J. Hazard. Mater. 137 (2006) 418-430.
[73] B. Adesola, K. Ogundipe, K.T. Sangosanya, B.D. Akintola, A. Oluwa, E. Hassan, Comparative study on
CE

the biosorption of Pb(II), Cd(II) and Zn(II) using Lemon grass (Cymbopogon citratus): Kinetics, isotherms
and thermodynamics. , Chem. Int. 2 (2016) 89-102.
[74] A. Gupta, C. Balomajumder, Simultaneous adsorption of Cr(VI) and phenol onto tea waste biomass
from binary mixture: Multicomponent adsorption, thermodynamic and kinetic study, J. Environ. Chem.
AC

Eng. 3 (2015) 785-796.


[75] S. Pandey, S.B. Mishra, Organic–inorganic hybrid of chitosan/organoclay bionanocomposites for
hexavalent chromium uptake, J. Colloid Interface Sci. 361 (2011) 509-520.
[76] J. Iqbal, F. Cecil, K. Ahmad, M. Iqbal, M. Mushtaq, M. Naeem, T. Bokhari, Kinetic study of Cr (III) and
Cr (VI) biosorption using Rosa damascena phy-tomass: a rose waste biomass, Asian J. Chem. 25 (2013)
2099-2103.
[77] V.R. Remya, V.K. Abitha, P.S. Rajput, A.V. Rane, A. Dutta, Silver nanoparticles green synthesis: A mini
review, Chem. Int. 3 (2017) 165-171.

16
ACCEPTED MANUSCRIPT

[78] A. Shindy, Problems and solutions in colors, dyes and pigments chemistry: A Review, Chem. Int. 3
(2017) 97-105.
[79] H. Shindy, Basics in colors, dyes and pigments chemistry: A review, Chem. Int. 2 (2016) 29-36.
[80] C. Ukpaka, Development of model for bioremediation of crude oil using moringa extract, Chem. Int.
2 (2016) 19-28.
[81] C. Ukpaka, Predictive model on the effect of restrictor on transfer function parameters on
pneumatic control system, Chem. Int. 2 (2016) 128-135.
[82] C. Ukpaka, Empirical model approach for the evaluation of pH and conductivity on pollutant
diffusion in soil environment, Chem. Int. 2 (2016) 267-278.

T
[83] C. Ukpaka, C. Ukpaka, Characteristics of groundwater in Port-Harcourt local Government area,
Chem. Int. 2 (2016) 136-144.

IP
[84] C.P. Ukpaka, F.U. Igwe, Modeling of the velocity profile of a bioreactor: the concept of biochemical
process, Chem. Int. 3 (2017) 258-267.

CR
[85] E. Öbek, A. Şaşmaz, H. Hasar, The accumulation of heavy metals in Typha latifolia L. grown in stream
carrying secondary effluent, Ecol. Eng. 33 (2008) 278-284.
[86] A. Sasmaz, E. Obek, The accumulation of silver and gold in Lemna gibba L. exposed to secondary
effluents, Chem. Erde. Geochem. 72 (2012) 149-152.

US
[87] A. Sasmaz, M. Sasmaz, The phytoremediation potential for strontium of indigenous plants growing
in a mining area, Environ. Exp. Bot. 67 (2009) 139-144.
[88] M. Sasmaz, B. Akgül, A. Sasmaz, Distribution and accumulation of selenium in wild plants growing
naturally in the Gumuskoy (Kutahya) Mining Area, Turkey, Bull. Environ. Contam. Toxicol., 94 (2015) 598-
AN
603.
[89] M. Sasmaz, B. Akgul, D. Yıldırım, A. Sasmaz, Bioaccumulation of thallium by the wild plants grown in
soils of mining area, Int. J. Phytoremediat. 18 (2016) 1164-1170.
[90] M. Iqbal, Vicia faba bioassay for environmental toxicity monitoring: a review, Chemosphere. 144
M

(2016) 785-802.
[91] M. Iqbal, M. Abbas, M. Arshad, T. Hussain, A.U. Khan, N. Masood, M.A. Tahir, S.M. Hussain, T.H.
Bokhari, R.A. Khera, Gamma radiation treatment for reducing cytotoxicity and mutagenicity in industrial
ED

wastewater, Pol. J. Environ. Stud. 24 (2015) 2745-2750.


[92] M. Iqbal, Z. Ali, M.A. Qamar, A. Ali, F. Hussain, M. Abbas, J. Nisar, Nickel adsorption onto
polyurethane ethylene and vinyl acetate sorbents, Water Sci. Technol. 76 (2017) 219-235.
[93] M. Iqbal, I.A. Bhatti, Gamma radiation/H2O2 treatment of a nonylphenol ethoxylates: degradation,
PT

cytotoxicity, and mutagenicity evaluation, J. Hazard. Mater. 299 (2015) 351-360.


[94] M. Iqbal, N. Iqbal, I.A. Bhatti, N. Ahmad, M. Zahid, Response surface methodology application in
optimization of cadmium adsorption by shoe waste: A good option of waste mitigation by waste, Ecol.
CE

Eng. 88 (2016) 265-275.


[95] M. Iqbal, J. Nisar, Cytotoxicity and mutagenicity evaluation of gamma radiation and hydrogen
peroxide treated textile effluents using bioassays, J. Environ. Chem. Eng. 3 (2015) 1912-1917.
[96] M. Iqbal, J. Nisar, M. Adil, M. Abbas, M. Riaz, M.A. Tahir, M. Younus, M. Shahid, Mutagenicity and
AC

cytotoxicity evaluation of photo-catalytically treated petroleum refinery wastewater using an array of


bioassays, Chemosphere. 168 (2017) 590–598.
[97] A. Kanwal, H.N. Bhatti, M. Iqbal, S. Noreen, Basic Dye Adsorption onto Clay/MnFe2O4 Composite: A
Mechanistic Study, Water Environ. Res. 89 (2017) 301-311.

17
ACCEPTED MANUSCRIPT

T
IP
CR
US
AN
M
ED
PT
CE
AC

18
ACCEPTED MANUSCRIPT

T
IP
CR
US
AN
M
ED
PT
CE

Fig. 1: (A-F) Single metal adsorption system (A) Effect of metal ion concentration on adsorption of Zn
AC

(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

19
ACCEPTED MANUSCRIPT

T
IP
CR
US
AN
M
ED
PT
CE

Fig. 2: Effect of pH on adsorption of Zn (II) and Co (II) ions onto Pitpapra (A) leave , (B) stem
AC

(C) roots

20
ACCEPTED MANUSCRIPT

T
IP
CR
US
AN
M
ED
PT
CE

Fig. 3: Effect of contact time on adsorption of Zn (II) and Co (II) ions onto Pitpapra biomasses
AC

(A) leave, (B) stem and (C) root

21
ACCEPTED MANUSCRIPT

0.03
0.025
(A)
0.02

Ce/qe
0.015
0.01
y = 1E-05x + 0.0147
0.005 R² = 0.0007
0

T
0 10 20 30 40

IP
Ce (mg/L)

0.02

CR
(B)
0.015
Ce/qe

0.005
0.01
US y = 0.0002x + 0.0082
R² = 0.6569
AN
0
0 10 20 30 40
Ce (mg/L)
M

0.03
(C)
ED

0.02
PT Ce/qe

0.01 y = -7E-06x + 0.0223


R² = 0.0004

0
CE

0 10 20 30 40
Ce (mg/L)
AC

22
ACCEPTED MANUSCRIPT

0.008
(D)
0.006

Ce/qe
0.004
y = 0.0003x + 0.0023
0.002 R² = 0.9971

T
0 5 10 15 20
Ce (mg/L)

IP
0.025

CR
0.02
(E)
0.015
Ce/qe

0.01

0.005
US y = 0.0004x + 0.005
R² = 0.9655
AN
0
0 10 20 30 40 50
Ce (mg/L)
M
ED

0.015
(F)
0.01
Ce/qe
PT

0.005 y = 0.0002x + 0.0066


R² = 0.7531
CE

0
0 10 20 30
Ce (mg/L)
AC

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

23
ACCEPTED MANUSCRIPT

4
(A)

log qe (mg/g)
3

1 y = 0.9003x + 1.9665
R² = 0.8069
0
0 0.5 1 1.5 2

T
log Ce (mg/L)

IP
4
(B)

CR
3
log qe (mg/g)

1 US
y = 0.8079x + 2.1753
R² = 0.9483
AN
0
0 0.5 1 1.5 2
log Ce (mg/L)
M

4
(C)
log qe (mg/g)

3
ED

2
y = 1.0715x + 1.5682
R² = 0.926
PT

0
0 0.5 1 1.5 2
CE

log Ce (mg/L)
AC

24
ACCEPTED MANUSCRIPT

4
(D)

log qe (mg/g)
3

1 y = 0.6018x + 2.653
R² = 0.969
0

T
0 0.5 1 1.5
log Ce (mg/L)

IP
CR
4
(E)
log qe (mg/g)

1
US y = 0.5794x + 2.4462
R² = 0.9355
AN
0
0 0.5 1 1.5 2
log Ce (mg/L)
M

4
(F)
ED
log qe (mg/g)

2
y = 0.8234x + 2.2436
PT

1 R² = 0.9688

0
CE

0 0.5 1 1.5
log Ce (mg/L)
AC

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

25
ACCEPTED MANUSCRIPT

T
IP
CR
US
Fig. 6: FTIR spectra (A) leave biomass before adsorption, (B) leaves biomass after adsorption,
AN
(C) stem biomass before adsorption and (D) stem biomass after adsorption
M
ED
PT
CE
AC

26

Das könnte Ihnen auch gefallen