Water Air Soil Pollut (2018) 229:257

https://doi.org/10.1007/s11270-018-3906-y

Competitive Adsorption of Heavy Metals from Aqueous

Solution onto Oxidized Activated Carbon Fiber
Maria Selene Berber-Mendoza & Jesús Ivan Martínez-Costa &
Roberto Leyva-Ramos & Hector Javier Amezquita Garcia &
Nahúm Andrés Medellín Castillo

Received: 15 March 2018 / Accepted: 4 July 2018

# Springer Nature Switzerland AG 2018

Abstract In this study, the competitive adsorption of higher than that of the Ni(II). Nevertheless, in the com-
Ni(II)–Pb(II) and Ni(II)–Zn(II) on oxidized activated petitive adsorption, the affinity of Pb(II) towards the
carbon fiber (ACF-Ox) from aqueous solutions was ACF-Ox was far greater than that of the Ni(II).
studied. The experimental competitive adsorption data
were interpreted by the following multicomponent ad-
sorption isotherms: non-modified, extended, and modi- Keywords Competitive adsorption . Oxidized activated
fied Langmuir; non-modified and modified Redlich- carbon fiber . Heavy metal . Multicomponent isotherms
Peterson; extended Freundlich; and Sheindorf-Rebuhn-
Sheintuch. The extended Freundlich multicomponent Nomenclature
isotherm best fitted the adsorption data for both systems ai Redlich-Peterson isotherm constant for metal i
Ni(II)–Pb(II) and Ni(II)–Zn(II) onto ACF-Ox. The sin- (L/g)
gle metal adsorption on ACF-Ox showed that the Ni(II) aij Competition coefficient of component i by
adsorption capacity was 1.12 times greater than that of component j
Zn(II); however, in the competitive adsorption, the bi Redlich-Peterson isotherm constant for metal i
Zn(II) presented an intense antagonism to the adsorption (L/meq)βι
of Ni(II) and Ni(II) to Zn(II) too. The single-adsorption Ci Concentration of metal i in aqueous solution at
isotherms of Pb(II) and Ni(II) on ACF-Ox revealed that equilibrium (meq/L)
the selectivity of Pb(II) towards ACF-Ox was slightly Ci,exp Experimental concentration of metal i (meq/L)
Ci,F Final concentration of metal i in aqueous solu-
tion at equilibrium (meq/L)
M. S. Berber-Mendoza (*) : N. A. Medellín Castillo
Ci,0 Initial concentration of metal i in aqueous so-
Centro de Investigación y Estudios de Posgrado, Facultad de lution (meq/L)
Ingeniería, UASLP, Av. Dr. Manuel Nava No. 8, SLP 78290 San %D Average percentage deviation
Luis Potosi, Mexico Ki Langmuir isotherm constant of metal i (L/meq)
e-mail: selene.berber@uaslp.mx
KE,i Extended Langmuir multicomponent isotherm
J. I. Martínez-Costa : R. Leyva-Ramos constant for component i (L/meq)
Centro de Investigacion y Estudios de Posgrado, Facultad de ki Freundlich isotherm constant for metal i
Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, (meq(1–1/n) L(1/n)/g)
Av. Dr. N. Nava No. 6, SLP 78210 San Luis Potosi, Mexico
m Mass of ACF-Ox (g)
H. J. Amezquita Garcia N Number of metals in solution
Facultad de Ciencias Quimicas, Universidad Autonoma de Nuevo Nm Number of experiment data
Leon, Monterrey, Nuevo Leon, Mexico ni Freundlich isotherm constant for metal i
257 Page 2 of 15
qi Uptake of metal i adsorbed per mass of ACF-
Ox (meq/g)
qi,j,cal Uptake of metal of i corresponding to data
number j calculated with the multicomponent
adsorption isotherm (meq/g)
qi,j,exp Experimental uptake of metal i corresponding
to data number j (meq/g)
qm,i Langmuir isotherm constant for metal i (meq/g)
qmax Constant of extended Langmuir multicompo-
nent isotherm (meq/g)
V0 Initial volume of solution (L)
xi, yi, Extended Freundlich multicomponent isotherm
zi constants for component i
Greek Letters
βi Redlich-Peterson isotherm constant for metal i
ηi Interaction factor for metal i
1 Introduction
The pollution of water by heavy metals is mainly attrib-
uted to anthropogenic activities of different industrial
processes such as electroplating, galvanizing, textile
manufacturing, tanneries, pigment manufacturing, metal-
lurgical facilities, and paint production (Taşar et al. 2014).
Wastewater from these industries contains Pb(II), Ni(II),
and Zn(II), and the presence of these metals in wastewater
is of serious concern because some of these metals are
very toxic to the health of human beings, other biological
species, and environment. Many physicochemical
methods have been developed for the removal of heavy
metals from aqueous solutions, but most of these methods
have significant disadvantages. In comparison with con-
ventional technologies such as chemical precipitation, ion
exchange, membrane filtration, electrolytic methods, and
solvent extraction, adsorption is regarded as a very effec-
tive and attractive process with several advantages asso-
ciated with not chemical sludge and high removal effi-
ciency. Among the most commonly used adsorbents are
activated carbon, biosorbents, and natural zeolites and
clays (Padilla-Ortega et al. 2013; Zhu et al. 2012).
The activated carbon fiber (ACF) is a novel adsor-
bent that can be used for removing organic as well as
heavy metal pollutants from municipal and industrial
wastewaters. The adsorption capacity of ACF towards
heavy metals can be enhanced by oxidizing the ACF
(ACF-Ox) using a nitric acid solution (Berber-Mendoza
et al. 2013). Several studies on metal adsorption on ACF
Water Air Soil Pollut (2018) 229:257
have been focused on the adsorption of a single metal
ion; however, wastewater is a complex mixture contain-
ing more than one metal ion. The presence of another
metal in the solution affects the adsorption capacity of a
single metal. Hence, it is crucial to study the competitive
adsorption of heavy metals on ACFs and to find out
about the selectivity or affinity of each metal for a given
ACF and if there is competition between the metal
cations for the same adsorption sites.
The competitive adsorption of heavy metals from
aqueous solutions has been investigated for various
metal-adsorbent systems. Some of the systems include
Pb(II)–Cu(II)–Zn(II) onto xanthate-modified magnetic
chitosan (Zhu et al. 2012), Cu(II)–Ni(II)–Cd(II) on peat
(Liu et al. 2008), Cu(II)–Pb(II)–Ni(II) using chitosan
immobilized on bentonite (Futalan et al. 2011), Pb(II)–
Cd(II)–Zn(II) on Eichhornia crassipes (Mahamadi and
Nharingo 2010), Cd(II)–Ni(II), Zn(II)–Cd(II), and
Pb(II)–Cu(II) on bentonite, sepiolite, and vermiculite,
respectively (Padilla-Ortega et al. 2013). Some authors
reported that in the competitive adsorption of Cd(II)–
Ni(II) on bentonite, each metal presented very similar
antagonism towards the adsorption of the other metal;
however, the Zn(II) strongly affected the adsorption of
Cd(II) on sepiolite, but Cd(II) did not influence the
adsorption of Zn(II). Finally, the affinity of Pb(II) to-
wards the vermiculite was much higher than that of the
Cu(II) (Padilla-Ortega et al. 2013).
The single metal adsorption of Cd(II) and Pb(II) on
several types of ACFs has been extensively investigated
(Arcibar-Orozco et al. 2014; Babic et al. 2002; Leyva-
Ramos et al. 2011; Leyva et al. 2008; Rangel-Mendez
and Streat 2002), and it has been demonstrated that the
adsorption capacity of the ACFs towards these heavy
metals can be enhanced by increasing the pH and tem-
perature of the solution. Additionally, a few works have
been focused on studying the single metal adsorption of
Ni(II) and Zn(II) from aqueous solutions on ACFs
(Álvarez-Merino et al. 2005; Faur-Brasquet et al. 2002;
Kadirvelu et al. 2000; Park et al. 2004; Shim et al. 2001).
On the other hand, the ACF was pretreated with 1.0 M
HNO3 and KOH to remove Cu(II) and Cd(II) and the
time contact was 240 min; however, the data was not
adjusted to a kinetic model (Kang et al. 2008), the
adsorption kinetics of Pb(II) onto an oxidized activated
carbon fiber were studied and found to be better de-
scribed by the pseudo-second order model (Mena
Aguilar et al. 2016). Nevertheless, no study regarding
the competitive adsorption of these metal ions from
Water Air Soil Pollut (2018) 229:257 Page 3 of 15 257

water solutions onto ACF has been reported in the tech- (c) Modified Langmuir multicomponent isotherm
nical literature (Berber-Mendoza et al. 2013; Faur et al. (MLMI) with an interaction factor ηi (Srivastava
2005; Masson et al. 2016; Mena Aguilar et al. 2016). et al. 2006a, b, 2008):
This work was aimed at studying the competitive
adsorption of Ni(II)–Pb(II) and Zn(II)–Ni(II) on an qm;i K i ðC i =ηi Þ
ACF oxidized with a nitric acid solution (ACF-Ox). qi ¼ ð6Þ
1 þ ∑Nj¼1 K j ðC i =ηi Þ
Furthermore, the effect of the presence of Ni(II) on the
adsorption of Zn(II) on ACF-Ox and vice versa was also
investigated in detail.
(d) Non-modified Redlich-Peterson multicomponent
isotherm (NRPMI) (Srivastava et al. 2006b, 2008):

2 Single and Multicomponent Adsorption

ai C i
Equilibrium Isotherms qi ¼ β
ð7Þ
1 þ ∑Nj¼1 b j C j j
The adsorption equilibrium data for an individual metal
can be usually represented by the Langmuir, Freundlich,
and Redlich-Peterson isotherms, which are expressed as (e) Modified Redlich-Peterson multicomponent iso-
follows: therm (MRPMI) with an interaction factor ηi
(Srivastava et al. 2006b):
1=ni
qi ¼ k i C i ð1Þ
ai ðC i =ηi Þ
qm;i K i C i qi ¼
β j ð8Þ
qi ¼ ð2Þ 1þ ∑Nj¼1 b j C i =η j
1 þ K iCi

ai C i
qi ¼ β
ð3Þ (f) Extended Freundlich multicomponent isotherm
1 þ bi C i i (EFMI) (Papageorgiou et al. 2009; Srivastava
et al. 2006b):
The multicomponent adsorption isotherms have been
advanced from the single-component adsorption iso-


therms and can be classified according to the single- 1
n1 þx1 1
n2 þx2
adsorption isotherm that originated the multicomponent K1C K2C
qi ¼ x 1 1 q2 ¼ x 2 2 ð9Þ
isotherm. In this work, the experimental binary adsorp- C 1 þ y1 C z11 C 2 þ y2 C z12
tion data were interpreted using the following multicom-
ponent adsorption isotherms:
(g) Sheindorf-Rebuhn-Sheintuch isotherm (SRSI)
(a) Non-modified Langmuir multicomponent isotherm (Sheindorf et al. 1981):
(NLMI) (Papageorgiou et al. 2009):


! n1 −1
N i
qm;i K i C i
qi ¼ ð4Þ qi ¼ k i C i ∑ aij C j ð10Þ
1 þ ∑Nj¼1 K j C j j¼1

where aii = ajj = 1.

(b) Extended Langmuir multicomponent isotherm The following function was minimized to estimate
(ELMI) (Yang 1987): the competition and interaction factors of the multicom-
ponent isotherms:

2 Nm
2
qmax K E;i C i
qi ¼ ð5Þ
1 þ ∑Nj¼1 K E; j C j Least squares ¼ ∑ ∑ qi; j;exp −qi; j;cal ð11Þ
i¼1 j¼1
257 Page 4 of 15 Water Air Soil Pollut (2018) 229:257

The Micromath Scientist software minimized the method using a surface area and porosimetry analyzer,
above function using the algorithm of Levenberg- Micromeritics, model ASAP 2020.
Marquardt. Besides, the average percentage deviation The active sites of the adsorbent were determined by
was computed from with the subsequent equation: an acid-base titration method proposed by Boehm (1994).
"  # The total basic sites were neutralized with a 0.1 N HCl
Nm  
1 i¼2 1  qi; j;exp −qi; j;cal  solution, and the total acid sites, including the carboxylic,
%D ¼ ∑ ∑   100% ð12Þ
2 i¼1 N m j¼1  qi; j;exp  hydroxylic and lactonic sites, were titrated using a 0.1 N
NaOH solution. The carboxylic and lactonic sites were
titrated using 0.1 N Na2CO3 solution and carboxylic sites
were titrated using 0.1 N NaHCO3 solution. The hydrox-
3 Materials and Methods ylic sites were evaluated by subtracting the carboxylic
and lactonic sites from the total acidic sites. The concen-
3.1 Activated Carbon Fiber trations of acidic and basic sites are listed in Table 2.
The pH of the point of zero charge (pHPZC) of the
The ACF-Ox used throughout this study was chosen ACF-Ox was determined by a similar procedure as that
based on a previous work (Berber-Mendoza et al. 2013). reported by (Babic et al. 1999) and (Berber-Mendoza
The ACF-Ox selected exhibited the highest adsorption et al. 2013). The pHPZC of the ACF-Ox was 3.42
capacity towards Ni(II), Zn(II), and Pb(II) from aqueous (Berber-Mendoza et al. 2013). This value was corrobo-
solutions. rated by the fact that the concentration of total acidic sites
was nearly 6.5 higher than that of basic sites (see Table 2).
3.2 Oxidation of Activated Carbon Fiber

The ACF used is produced from polyacrylonitrile by
KoTHmex. The ACF was oxidized by a procedure
reported elsewhere (Leyva-Ramos et al. 2011). Briefly,
500 mL of 15% v/v HNO3 solution and 20 g of ACF
were poured into a 1-L glass flask. The acid solution
containing the ACF was heated for 2 h on a heating
plate, and keeping the temperature below 50 °C. After-
ward, the solution was allowed to cool and then drained.
The ACF-Ox was rinsed several times with deionized
water until the pH of the rinsing solution did not vary
over time. The ACF-Ox was dried in an oven at 110 °C
for 24 h and was stored in a container.
3.4 Determination of the Heavy Metal Concentrations
in Aqueous Solutions
The concentrations of Pb(II), Ni(II), and Zn(II) in aque-
ous solutions were determined by using an atomic ab-
sorption spectrophotometer, Varian, model spectrAA-20
and the concentration of each metal in the solution was
calculated from a calibration curve prepared using 4–6
standard solutions. The metal solutions were prepared
using Pb(NO3)2, Ni(NO3)2∙6H2O, and Zn(NO3)2 6H2O.
The solution pH was adjusted with 0.01 M HNO3 and
0.01 M NaOH solutions.

3.3 Characterization of the ACF-Ox
The textural properties shown in Table 1 (surface area =
1156 m2/g, pore volume = 0.574 cm3/g, and mean pore
diameter = 1.97 nm) were determined by the N2-BET
3.5 Method for Obtaining the Adsorption Equilibrium
Data
The experimental adsorption equilibrium data for the
single and binary systems were obtained in a batch

Table 1 Textural properties of ACF-Ox

Surface Pore volume Average pore Pore volume distribution

area (m2/g) (cm3/g) diameter (nm)
Micropores (%) Mesopores (%) Macropores (%)

< 2 nm 2 < d < 4 nm 4 < d < 50 nm d > 50 nm

1156 0.574 1.968 65.95 29.48 4.13 0.43

Water Air Soil Pollut (2018) 229:257 Page 5 of 15 257

Table 2 Physicochemical prop-

erties of ACF-Ox Acidic sites Total basic
sites (meq/g)
Carboxylic (meq/g) Lactonic (meq/g) Phenolic (meq/g) Total (meq/g)

0.596 0.332 0.900 1.828 0.280

adsorber. A volume of 40 mL of an aqueous solution of a
known initial concentration of single or binary metals
and 0.3 g of ACF-Ox were added to the 50-mL conical
vial, which served as the adsorber. The adsorber solution
was shaken by placing the adsorber in an orbital shaker
during 15 min twice a day, and the solution pH was
periodically adjusted by adding few drops of 0.1 N
HNO3 and NaOH solutions. The adsorber was placed
in a thermostatic bath, and the adsorbent and metal
solutions were in contact until equilibrium was attained
in approximately 7 days. Subsequently, the solution was
filtered, and a 10-mL aliquot was taken to evaluate its
final concentration using the method previously de-
scribed. The uptake of each metal adsorbed was calcu-
lated by performing a mass balance of metal i, which
that can be mathematically expressed as:
 
V 0 C i;0 −C i; F
qi ¼ ð13Þ
m lowest %D. As shown in Table 3, the Redlich-
4 Results and Discussion
4.1 Single-Adsorption Isotherms
The experimental single-adsorption equilibrium data
were obtained to compare the affinity of each metal for
the ACF-Ox. At T = 25 °C, the single metal adsorption
isotherms of Zn(II) and Ni(II) were determined at pH =
6 and those of Pb(II) and Ni(II) at pH = 4 on ACF-Ox.
The solution pH was chosen as the pH at which the
ACF-Ox presented the maximum adsorption capacity
towards one of the metal cations (Berber-Mendoza et al.
2013), but without precipitating any of the metals
existing in the solution.
The single Langmuir, Freundlich, and Redlich-
Peterson isotherm models were fitted to the experi-
mental adsorption equilibrium data. These isotherm
models are commonly applied for interpreting the
individual adsorption isotherms. The values of the
isotherm constants and average percentage deviations
(%D) for these isotherms are listed in Table 3. The
values of %D varied from 8.27 to 15.5%, 7.02 to
17.4%, and 2.98 to 11.8% for the Langmuir,
Freundlich, and Redlich-Peterson isotherm models,
respectively. The isotherm model best fitting the ex-
perimental data was assumed to be that having the
Peterson isotherm provided the optimum fit in all the
single metal isotherm cases. This result can be ex-
plained recalling that the Redlich-Peterson isotherm
model has three parameters, whereas Freundlich and
Langmuir isotherm models only have two.
At T = 25 °C, the experimental adsorption equilibri-
um data and the single-adsorption isotherms of Ni(II),
Zn(II), and Pb(II) onto ACF-Ox are plotted in Fig. 1a, b.
Figure 1a shows that at pH = 4 and a metal concentration
at equilibrium of 3.0 meq/L, the adsorption capacity of
ACF-Ox towards Pb(II) is 1.26 times greater than that of

Table 3 Parameter values of the Langmuir, Freundlich, and Redlich-Peterson isotherms for the single metal adsorption on ACF-Ox at T =
25 °C

Metal pH Langmuir Freundlich Redlich-Peterson

qm (meq/g) K (L/meq) %D K (meq1–1/n L1/n/g) N %D a (L/meq) b (L/g)β β %D

Ni 6 0.716 77.56 15.5 0.704 5.76 16.4 108.1 149.9 0.903 5.29
Zn 0.693 57.55 12.9 0.572 5.99 17.4 75.72 120.8 0.903 11.0
Pb 4 0.413 133.0 14.7 0.469 5.84 16.9 112.4 245.5 0.892 11.8
Ni 0.394 8.995 8.27 0.319 4.58 7.02 8.83 25.60 0.855 2.98
257 Page 6 of 15 Water Air Soil Pollut (2018) 229:257

Fig. 1 Single-adsorption 0.60

isotherms of a Pb(II) and Ni(II) on
ACF-Ox at pH = 4 and b Ni(II)
and Zn(II) on ACF-Ox at pH = 6. 0.50

Metal uptake on ACF-Ox, meq/g

The lines represent the Redlich-
Peterson isotherm at T = 25 °C
0.40

0.30

0.20
Pb(II)
Ni(II)
0.10

0.00
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00
Concentrantion of the metal at equilibruim, meq/L
a)

1.0

0.8
Metal uptake on ACF-Ox, meq/g

0.6

0.4
Ni(II)
Zn(II)
0.2

0.0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00
Concentrantion of the metal at equilibruim, meq/L

b)

Ni(II), which means that ACF-Ox is more selective for
Pb(II) than for Ni(II). As depicted in Fig. 1b, at pH = 6
and a metal concentration at equilibrium of 4.0 meq/L,
the uptake of Ni(II) adsorbed was 1.12 times larger than
that of Zn(II). This difference was not significant and
revealed that the affinity of ACF-Ox for Ni(II) was
almost the same as that for Zn(II).
The metal cations were mainly adsorbed on the acidic
sites of ACF-Ox and predominantly on the carboxylic
sites since the adsorption was carried out at pH below 6
(Berber-Mendoza et al. 2013). The capacity of the ACF-
Ox towards any of the metal cations was high because of
the elevated concentration of acidic sites in the ACF-Ox
(see Table 2).
The electronegativities of Pb(II) and Ni(II) and the
hydrated ionic radius are very similar (see Table 4).
Therefore, these characteristics are not relevant when
explaining the differences on the adsorption capacities
Water Air Soil Pollut (2018) 229:257 Page 7 of 15 257

Table 4 Physicochemical properties of Pb(II), Ni(II), and Zn(II) ACF-Ox were interpreted using the multicomponent
Parameter Cation adsorption isotherm models previously described. The
values of the parameters and the average percentage
Pb(II) Ni(II) Zn(II) deviation (%D) of each model are shown in Table 5.
As in the case of the individual isotherm models, the
Electronegativity 1.87 1.91 1.65
model yielding the lowest %D was considered as the
Ionic radius, Å 1.20 0.78 0.74
model that best fitted the experimental data.
Hydrated ionic radius 4.01 4.04 4.30 The %D values given in Table 5 indicated that the
(Nightingale 1959) Å
extended Langmuir multicomponent isotherm (ELMI)
did not fit the experimental data because the values of
%D ranged from 31 to 55%. This result was probably due
of the ACF-Ox towards Pb(II), Ni(II), and Zn(II). How-
to that all the parameters of the ELMI were estimated by
ever, Pb(II) has an ionic radius 1.54 times greater than
fitting the multicomponent adsorption equilibrium data,
Ni(II), which means that the hydration layer of Pb(II) is
and no information was required from the single metal
weak compared to Ni(II) and could be displaced much
Langmuir isotherm. Furthermore, the non-modified
easier, so it interacts in a much stronger way with the
Langmuir multicomponent isotherm (NLML) and the
surface of the ACF-Ox and consequently Pb(II) is more
modified multicomponent Langmuir isotherm (MLMI)
selective than Ni(II) on ACF-Ox. On the other hand,
moderately fitted the experimental data since the %D
Ni(II) and Zn(II) ionic radius are very similar and there-
varied from 19 to 30% and 18 to 30%, respectively.
fore the metal uptake too as show in Fig. 1b.
The experimental data was also interpreted by the
modified Redlich-Peterson multicomponent isotherm
4.2 Competitive Adsorption Isotherms (MRPMI) and non-modified (NRPMI), and the %D for
MRPMI and NRPMI varied from 23 to 29% and 16 to
In this work, the competitive adsorption equilibrium 27%, correspondingly. Hence, the %D was smaller for
data for the systems Ni(II)–Pb(II) and Ni(II)–Zn(II) on the NRPMI than that for the MRPMI (see Table 5). These

Table 5 Parameters of the multicomponent isotherm models for the binary adsorption of the Pb(II)–Ni(II) and Ni(II)–Zn(II) systems on
ACF-Ox

Model Single Interaction Ni(II)–Pb(II) Ni(II)–Zn(II)

isotherm factors
parameters Parameters %D Parameters %D

NLMI 4 0 30 19
MLMI 4 2 ηPb = 1.212 30 ηNi = 2.16 18
ηNi = 1.483 ηZn = 3.54
ELMI 0 3 qmax = 0.389 31 qmax = 0.732 55
Ke,Ni = 6.99 Ke,Zn = 43.1
Ke,Pb = 142 Ke,Cd = 61.2
NRPMI 6 0 27 16
MRPMI 6 2 ηPb = 1.324 29 ηNi = 1.122 23
ηNi = 1.875 ηZn = 1.074
EFMI 4 6 xNi = 0.529 14 xZn = 0.899 13
yNi = 2.04 yZn = 1.045
zNi = 0.322 zZn = 1.113
xPb = 0.507 xNi = 0.114
yPb = 0.223 yNi = 1.027
zPb = 0.327 zNi = 0.298
SRSI 4 4 aPb,Pb = 1 25 aNi,Ni = 1 21
aPb,Ni = 0.07 aZn,Ni = 1.806
aNi,Ni = 1 aZn,Zn = 1
aNi.Pb = 8.09 aNi,Zn = 1.313
257 Page 8 of 15 Water Air Soil Pollut (2018) 229:257

Fig. 2 Comparison between the 0.6

metal uptake predicted with the
best model and the experimental
metal uptake. a Ni(II)–Pb(II) and 0.5

Metal uptake predicted, meq/g

b Zn(II)–Ni(II) on ACF-Ox qpred = 1.1qexp
0.4
qpred = qexp
0.3 qpred = 0.9qexp

0.2

EFMI
0.1
Pb(II)
Ni(II)
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Experimental Metal uptake, meq/L
a)

0.6

0.5
Metal uptake predicted, meq/g

qpred = 1.1qexp
0.4
qpred = qexp
0.3 qpred = 0.9qexp

0.2

0.1 EFMI
Zn(II)
Ni(II)
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Experimental Metal uptake, meq/L
b)

results were not expected because the NRPMI has no
interaction parameters whereas the MRPMI has two
interaction parameters. In other words, the fitting param-
eters of MRPMI were 8 whereas those of NRPMI were 6.
The interpretation of the experimental binary adsorp-
tion data was also performed using the multicomponent
isotherm models of the Freundlich type such as the
extended Freundlich multicomponent isotherm (EFMI)
and the Sheindorf-Rebuhn-Sheintuch isotherm (SRSI).
Both models use the parameters of the Freundlich
individual isotherm and the parameters of interaction.
Based on the values of %D, the EFMI was that best
fitting model since it presented the lowest value of %D.
This result could be due to that the EFMI has six
additional interaction factors whereas the SRSI has four
interaction factors (aij). Besides, the values of aij were
only 2 instead of 4 since a11 and a22 were fixed to 1.
To analyze the goodness of fit for the best model, the
metal uptake predicted with the best model, qpred, was
plotted against the experimental metal uptake, qexp, in
Water Air Soil Pollut (2018) 229:257 Page 9 of 15 257

Figs. 2a, b for the systems Ni(II)–Pb(II) and Ni(II)–
Zn(II), respectively. The straight lines corresponding to
qpred = qexp, qpred = 1.1 qexp, and qpred = 0.9 qexp were
also graphed as frames of reference. These straight lines
represent exact prediction, overpredicted with %D =
10% deviation and underpredicted with %D = 10%. As
seen in these figures, the EFMI model, which was the
best model, predicted the experimental data reasonably
well. In general, the values of the uptakes of Pb(II) and
Zn(II) were overpredicted, but in the case of the uptake
of Ni(II), some experimental values were found above
as well as below the line for exact prediction.
4.3 Competitive Adsorption of Ni(II)–Pb(II)
on ACF-Ox
The competitive adsorption surface of Pb(II) on ACF-
Ox for the system Ni(II)–Pb(II) is graphed in Fig. 3a.

Fig. 3 a Competitive adsorption

surface of Pb(II) on ACF-Ox in
the presence of Ni(II). The surface
is predicted with the EFMI model.
b Adsorption isotherms of Pb(II)
at different isoconcentrations of
Ni(II), pH = 4 and T = 25 °C

a)

0.5
Uptake of Pb (II) adsorbed, meq/g

0.4

0.3

0.2
Ni (II) eq = 0 meq/L
Ni (II) eq = 1.27 meq/L
0.1
Ni (II) eq = 3.63 meq/L
Ni (II) eq = 6.87 meq/L
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Concentration of Pb (II), meq/L

b)
257 Page 10 of 15 Water Air Soil Pollut (2018) 229:257

Fig. 4 a Competitive adsorption

surface of Ni(II) on ACF-Ox in
the presence of Pb(II). The
surface is predicted with the
EFMI model. b Adsorption
isotherms of Ni(II) at different
isoconcentrations of Pb(II), pH =
4, and T = 25 °C

a)

0.5
Uptake of Ni (II) adsorbed, meq/g

0.4

0.3

0.2
Pb(II) eq = 0 meq/L
Pb(II) eq = 0.2 meq/L
0.1 Pb(II) eq = 0.6 meq/L
Pb(II) eq = 1.1 meq/L

0.0
0 1 2 3 4 5 6 7 8

Concentration of Ni (II), meq/L

b)

This adsorption surface shows that the adsorption of
Pb(II) was slightly affected by the presence of Ni(II) in
the system. Additionally, as it is seen in Fig. 3b, the
adsorption capacity of ACF-Ox towards single Pb(II)
was 0.48 meq/g at a Pb(II) equilibrium concentration of
1.0 meq/L when Ni(II) was not present in the system
(CNi = 0.0 meq/L). However, the adsorption capacity
slightly declined by increasing the isoconcentration of
Ni(II) at equilibrium. For example, the adsorption ca-
pacity of ACF-Ox declined 20.8 and 31.3% when the
Water Air Soil Pollut (2018) 229:257 Page 11 of 15 257

Fig. 5 a Competitive adsorption

surface of Ni(II) on ACF-Ox in
the presence of Zn(II). The
surface is predicted with the
EFMI model. b Adsorption
isotherms of Ni(II) at different
isoconcentrations of Zn(II), pH =
6, and T = 25 °C

a)

1.0
Uptake of Ni (II) adsorbed, meq/g

0.8

0.6

0.4

Zn (II)eq = 0 meq/L
0.2
Zn (II)eq = 0.86 meq/L
Zn (II)eq = 3.0 meq/L
Zn (II)eq = 6.76 meq/L
0.0
0 1 2 3 4 5 6 7
Concentration of Ni (II), meq/L

b)

concentration of Ni(II) at equilibrium was 1.27 and significantly decreased by raising the concentration of
6.87 meq/L, respectively. Pb(II) in the aqueous solution. In this case, the uptake of
The adsorption surface plotted in Fig. 4a shows that Ni(II) adsorbed on ACF-Ox was 0.50 meq/g at a Ni(II)
the uptake of Ni(II) adsorbed on ACF-Ox was equilibrium concentration of 8 meq/L when there was
257 Page 12 of 15 Water Air Soil Pollut (2018) 229:257

Fig. 6 a Competitive adsorption

surface of Zn(II) on ACF-Ox in
the presence of Ni(II). The surface
is predicted with the EFMI model.
b Adsorption isotherms of Zn(II)
at different isoconcentrations of
Ni(II), pH = 6, and T = 25 °C

a)

1.0
Uptake of Zn (II) adsorbed, meq/g

0.8

0.6

0.4

Ni(II) eq= 0 meq/L

0.2
Ni(II) eq= 2.19 meq/L
Ni(II) eq= 4.27 meq/L
Ni(II) eq= 8.06 meq/L
0.0
0 2 4 6 8 10 12
Concentration of Zn (II), meq/L

b)

no Pb(II) in the solution (CPb = 0 meq/L). The capacity
of ACF-Ox for adsorbing Ni(II) diminished about
45.2% at an isoconcentration of Pb(II) of 1.1 meq/L
(see Fig. 4b).
The above results indicate that the Pb2+ cations were
highly antagonistic to the competitive adsorption of Ni2+
cations; however, the Ni2+ exhibited low antagonistic
behavior to the competitive adsorption of Pb2+. Both
metal cations compete for the same acidic sites of the
ACF-Ox, but the Pb2+ occupied more sites than the Ni2+.
4.4 Competitive Adsorption of Ni(II)–Zn(II)
on ACF-Ox
The adsorption capacity of ACF-Ox towards Ni(II) was
greatly affected by the presence of Zn(II) in the solution.
Water Air Soil Pollut (2018) 229:257 Page 13 of 15 257

Zn(II) 0=1.75 meq/L Zn(II) 0=9.37 meq/L

Total active sites, %

Total active sites, %

(a) (b)
Fig. 7 Percentage of total sites occupies on ACF-Ox when Ni(II) is displaced by Zn(II), black bars = qNi first equilibrium; light gray bars =
qNi second equilibrium; dark gray bars = qZn second equilibrium. At pH = 6 and T = 25 °C

This antagonistic behavior of Zn(II) to the competitive
adsorption of Ni(II) can be observed in Fig. 5a, and a
significant decrease in the capacity of ACF-Ox for
adsorbing Ni(II) was noticed even for low concentrations
of Zn(II) at equilibrium. Figure 5b shows the adsorption
isotherms of Ni(II) at various isoconcentrations of Zn(II),
and a drastic decrease was clearly noted in the adsorption
capacity of ACF-Ox towards Ni(II) by the presence of
Zn(II). At a concentration of Ni(II) at equilibrium of
6.0 meq/L, the capacity of ACF-Ox for adsorbing Ni(II)
was drastically declined from 0.95 to 0.53 meq/g when
the isoconcentration of Zn(II) was raised from 0.0 to
0.86 meq/L. This decrease represented a capacity reduc-
tion of 44.5%. The Ni(II) adsorption capacity of ACF-Ox
was further diminished from 44.5 to 59.6% by increasing
the concentration of Zn(II) at equilibrium from 0.86 to
3.0 or 6.76 meq/L.
The presence of Ni(II) in the solution also affects the
competitive adsorption of Zn(II) on ACF-Ox, as shown
in Fig. 6a. This figure shows that the uptake of Zn(II)

Ni(II)0=2.01 meq/L Ni(II)0=8.9 meq/L

Total active sites, %

(a) (b)
Fig. 8 Percentage of total sites occupies on ACF-Ox when Zn(II) is displaced by Ni(II), black bars = qZn first equilibrium; light gray bars =
qNi second equilibrium; dark gray bars = qZn second equilibrium. At pH = 6 and T = 25 °C
257 Page 14 of 15
adsorbed on the ACF-Ox was significantly decreased by
the presence and competition of Ni(II). Figure 6b shows
that the adsorption capacity of ACF-Ox towards Zn(II)
was considerably reduced by increasing the concentra-
tions of Ni(II) at equilibrium. At a concentration of
Zn(II) at equilibrium of 12.0 meq/L, the uptakes of
Zn(II) adsorbed on ACF-Ox were 0.88, 0.68, 0.55, and
0.4 meq/g for the concentrations of Ni(II) at equilibrium
of 0.0, 2.19, 4.27, and 8.06 meq/L, respectively. The
decrease in the adsorption capacity of the ACF-Ox
towards the Zn(II) corresponded to 21.1, 36.0, and
53.3%.
The Ni2+ and Zn2+ cations compete for the same
acidic sites and they essentially showed the same antag-
onistic behavior to the competitive adsorption of the
other metal cation.
4.5 Displacement of the Adsorption Equilibrium
In the case of the adsorption of Ni(II) and Zn(II), the
competitive adsorption capacity of the ACF-Ox was
very similar to both metal cations. A study of the dis-
placement of the adsorption equilibrium was conducted
to find out if Ni(II) and Zn(II) ions competed for the
same cationic sites or different sites. These studies were
performed by first adsorbing one of the metal cations on
the ACF-Ox, and once the adsorption equilibrium was
attained (first equilibrium), then the adsorbed metal
cations were displaced by the other cation to reach again
equilibrium (second equilibrium). The percentage of
sites occupies by Ni(II) and Zn(II) was evaluated ac-
cording to the total sites concentration of ACF-Ox
(1.828 meq/g).
Figures 7 and 8 illustrates the percentage of Ni(II)
and Zn(II) occupied sites by adsorption in first and
second equilibrium. Figure 7a shows that an initial
concentration of Zn(II) of 1.75 meq/L, the adsorption
percentage of occupied sites in the first equilibrium was
12% (black bars), but when the second equilibrium was
reached, the uptake capacity decreased slightly (light
gray bars), from 2.4 to 12.7% by Ni(II), the amount of
Zn(II) displaced depends on the initial concentration of
Ni(II). On the other hand, the total percentage of occu-
pied sites by both Ni(II) and Zn(II) increased between
15 to 22%, which indicates that there are some specific
sites where Zn(II) is adsorbed, and could be different
sites for the Ni(II) uptake.
Figure 7b displays the percentage of Zn(II) displaced
by Ni(II) for different initial concentration of Ni(II) with
Water Air Soil Pollut (2018) 229:257
an initial concentration of Zn(II) of 9.73 meq/L. For this
case, the occupied sites in first equilibrium by Zn(II) on
ACF-Ox were from 45 to 52% (black bars). When Ni(II)
were added to the system to different initial concentra-
tions, the Zn(II) is displaced again from 5 to 12.8%
(light gray bars). However, also, the total occupied sites
remain around 50%, which is possible due to a complete
saturation of the adsorption sites on the ACF-Ox, and
that both Ni(II) and Zn(II) could be adsorbed on the
same active sites.
On one hand, Fig. 8a depicts when Ni(II) is adsorbed
with an initial concentration of 2.1 meq/L. The occupied
sites is close to 15% (black bars), and when Zn(II) is
added to the same system, with different initial concen-
tration, the total occupied sites by Zn(II) decreases from
1 to 5% (dark gray bars), showing the highest displace-
ment when the concentration of Zn(II) is the highest
(13.2 meq/L).
On the other hand, when an initial concentration of
Ni(II) of 8.9 meq/L, the sites occupies in first equi-
librium were 37% of the total sites of ACF-Ox, as
could be seen on Fig. 8b, (black bars) and when Zn(II)
is added with different initial concentrations, the oc-
cupied sites by Ni(II) decreases from 3 to 16% (dark
gray bars), and the total occupied sites goes from 40
to 45%.
The above results indicate that both ions compete
for a fraction of the same active sites of the ACF-
Ox. Therefore, the adsorption capacity of ACF-Ox
towards metals in competition affects each other.
However, there are sites that are only available for
Ni(II) and others for Zn(II), since both adsorb on the
ACF-Ox.
5 Conclusions
In the competitive system Ni(II)–Pb(II), the adsorp-
tion capacity of Pb(II) is slightly affected by the
presence of Ni(II). However, the influence of Pb(II)
on the adsorption capacity of Ni(II) on the ACF-Ox is
much higher.
In the competitive system Ni(II)–Zn(II), both cat-
ions affect adsorption capacities in a similar way.
The adsorbed Ni(II) ions on the ACF-Ox are
displaced by Zn (II), obtaining up to 80% of
displaced Ni(II). The adsorbed Zn(II) ions on the
ACF-Ox are displaced by Ni(II), obtaining up to
69% of displaced Ni(II).
Water Air Soil Pollut (2018) 229:257
Funding Information This work was funded by Fondo de
Ciencia Basica SEP-CONACyT through grant no. SEP-61537
and Fondo de apoyo a la Investigación (FAI) C12-FAI-03-48.48.
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