Water Air Soil Pollut (2019) 230:73

https://doi.org/10.1007/s11270-019-4106-0

Ion Exchange Modeling of the Competitive Adsorption

of Cu(II) and Pb(II) Using Chemically Modified Solid
Waste Coffee
J. Botello-González & F. J. Cerino-Córdova & N. E. Dávila-Guzmán &
J. J. Salazar-Rábago & E. Soto-Regalado & R. Gómez-González & M. Loredo-Cancino

Received: 13 July 2018 / Accepted: 4 February 2019

# Springer Nature Switzerland AG 2019

Abstract The presence of potentially toxic metals such
as Cu(II) and Pb(II) in aquifers and industrial effluents
represents a serious health problem due to their high
toxicity, non-biodegradability, and ability to
bioaccumulate. In this study, the removal of these pol-
lutants individually and as a binary mixture has been
studied, using solid coffee waste modified with 0.6 M
citric acid as the adsorbent, and a mathematical model
based on the ion exchange mechanism was implement-
ed to elucidate the adsorption equilibrium. The charac-
terization of modified coffee waste showed a pH value
at the point of zero charge of 2.97 and a high concen-
tration of carboxylic groups, which are susceptible to
ion exchange. Furthermore, the quantification of inter-
changeable ions confirmed that the main mechanism of
adsorption is the ion exchange of metal ions with the
protons present on the adsorbent’s surface. The experi-
mental data of the individual and binary adsorption
equilibrium using a model based on a phenomenologi-
cal approach was analyzed. The phenomenological
model was compared with the Freundlich and Langmuir
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11270-019-4106-0) contains
supplementary material, which is available to authorized users.
J. Botello-González : F. J. Cerino-Córdova (*) :
N. E. Dávila-Guzmán : J. J. Salazar-Rábago :
E. Soto-Regalado : R. Gómez-González :
M. Loredo-Cancino
Facultad de Ciencias Químicas, Universidad Autónoma de Nuevo
León, Av. Universidad s/n Cd. Universitaria, 66455 San Nicolás
de los Garza, Nuevo León, Mexico
e-mail: felipe.cerinocr@uanl.edu.mx
empirical solid-liquid adsorption models. The results
showed that the adsorption capacities of Cu(II) and
Pb(II) individually were 1.46 and 1.18 meq/g, and in a
binary mixture were 1.43 and 1.24 meq/g, respectively,
at pH 5 and 30 °C. In addition, the separation coeffi-
cients from ion exchange model revealed the predomi-
nance of protons as an exchangeable ion, which is in
accordance with the experimental evidence. Finally, the
correlation coefficient showed that the proposed model
predicts accurately the adsorption equilibrium.
Keywords Mathematical modeling . Ion exchange .
Binary mixture . Coffee residues . Chemical modification
1 Introduction
Water is a vital substance for all living beings on earth
and the contamination of water resources with heavy
metals or potentially toxic metals (Pourret and Bollinger
2018) is a real global problem that affects many coun-
tries that are increasingly industrialized seeking the
prosperity of their citizens. Industries are the biggest
source of water pollution; in some cases, the effluent
from your water treatment plants contains a potentially
toxic metal concentration that exceeds the maximum
concentration allowed in the international standards of
wastewater discharge in the bodies of water (Singh and
Kaushal 2013). Environmental Protection Agency
(USEPA) establishes the allowed concentrations of
0.04 and 0.0005 meq/L for Cu(II) and Pb(II), respec-
tively, and the disposal standard values in Mexico
 73 Page 2 of 14
allowed in discharge effluents are 0.13–0.19 meq/L for
Cu(II) and 0.002–0.01 meq/L for Pb(II), NOM-001-
SEMARNAT-1996 (Secretaría de Medio Ambiente y
Recursos 2003). Potentially toxic metals represent a
health hazard due to their accumulation, non-biodegrad-
ability, and toxicity characteristics. Long-term exposure
to copper may cause nose, mouth and eye irritations,
headache, stomachache, diarrhea, and dizziness. Fur-
thermore, the long-term exposure to lead may cause
gastrointestinal complications, hypertension, fatigue,
hemolytic anemia, abdominal pain, nausea, constipa-
tion, weight loss, cognitive dysfunction, and depression
(Sawyer et al. 2003).
In the interest of removing potentially toxic metals
from water, there are several treatment methods such as
chemical precipitation, ultra-filtration, ion flotation,
electro-coagulation, electrodialysis, sedimentation, and
membrane separation, to name a few. These methods
have some disadvantages such as their high operating
cost, high waste generation, and low removal efficiency
at low pollutant concentration (Kaur et al. 2012). The
use of adsorption processes is one of the alternatives that
have been investigated, due to its effectiveness in the
removal of potentially toxic metals at low concentra-
tions, low cost, and ease of operation (Sud et al. 2008).
The cost of this process can be reduced using adsorbents
of organic origin such as algae, bacteria, fungi, and agro-
industrial residues. These biomasses have some advan-
tages such as low cost, high availability, and low envi-
ronmental impact (Won et al. 2014; Yu et al. 2014).
Coffee waste is among the agro-industrial residues
that have been used as adsorbents. Coffee is one of the
most consumed beverages in the world and it is the
second most traded commodity after oil (Murthy and
Madhava Naidu 2012). The International Coffee Orga-
nization reported a global consumption of 2.9 gigatons
of soluble coffee during the years 2016 and 2017 (OIC
2017), which results in the generation of millions of tons
of coffee waste that are discarded to the environment.
Due to its high availability, several investigations have
been focused on evaluating its potential use as an ad-
sorbent material, and it had been demonstrated that
coffee waste has higher adsorption capacity than acti-
vated carbon, which is a commercial adsorbent widely
used in wastewater treatment (Davila-Guzman et al.
2016; Kyzas 2012).
In recent years, several studies have been conducted
to increase the potentially toxic metal adsorption capac-
ity of coffee waste by chemical modifications. Cerino-
Water Air Soil Pollut (2019) 230:73
Córdova et al. (2013a, b) carried out a batch study for
the removal of Pb(II) and Cu(II) on coffee waste chem-
ically modified with citric acid. The researchers showed
some important facts: the chemically modified coffee
waste had adsorption capacities of 3.2 and 8.1 times
higher than the unmodified material for Pb(II) and
Cu(II), respectively. This was explained considering
the significant increase of carboxylic groups after the
chemical treatment. In this research, the concentration of
acidic sites of the modified coffee waste was increased
from 1.74 to 4.69 meq/g and the maximum adsorption
capacities for Pb(II) and Cu(II) were 0.77 and 1.53 meq/
L, respectively, at pH 5.
Additionally, an ion exchange adsorption mechanism
for the removal of potentially toxic metals by unmodi-
fied coffee waste was proposed by Dávila-Guzmán et al.
(2013). The proposed mechanism is based on ion ex-
change reactions between the Cu(II) ions in the aqueous
solution and Ca(II) ions and protons in the surface of the
solid coffee waste. The number of copper ions adsorbed
was found to be equivalent to the number of ions re-
leased from the surface of the adsorbent at different
initial metal concentrations. The maximum adsorption
capacity obtained was 0.21 mmol/g.
However, most of the wastewater discharges contain
more than one potentially toxic metal ion; thus, the
adsorption isotherm model in a multicomponent system
is more complex than isotherms of a single adsorbate.
The adsorption isotherm models of two or more adsor-
bates are obtained by coupling the equations of the
individual isotherms to binary or multicomponent sys-
tems. Some of the most widely used competitive ad-
sorption models are the Langmuir and Freundlich
models. These models emerged from the study of gas
adsorption in solids; therefore, they are considered as
empirical models for the adsorption in the liquid phase.
Nevertheless, the empirical models do not provide phe-
nomenological information about the adsorption
process.
In some studies, mathematical models based on ion
exchange have been proposed for the multicomponent
adsorption of metals using algae as adsorbent material
(Chong and Volesky 1995; da Silva et al. 2015;
Sulaymon et al. 2013). In the literature analysis, it was
found that there are no competitive adsorption studies
using agro-waste materials as adsorbent of potentially
toxic metals (Das Graças Nunes Matos et al. 2009;
Kononova et al. 2015; Oliveira et al. 2008a, b;
Tokimoto et al. 2005; Utomo and Hunter 2006). The
Water Air Soil Pollut (2019) 230:73
aim of this study is to propose an ion exchange model
for the simultaneous adsorption of Cu(II) and Pb(II) in
aqueous solution onto solid coffee waste chemically
modified in batch system.
2 Materials and Methods
2.1 Chemical Modification of Coffee Waste
The coffee waste (CW) was collected as a by-product of
brewing coffee with an average particle size < 1 mm. Its
pretreatment and subsequent chemical modifications
were carried out according to a similar method described
by Vaughan et al. (2001). CW was washed several times
with distilled water, going from being a brown to a
colorless solution. Then, it was dried in an oven at
50 °C for 24 h. The CW obtained was stored in a closed,
dry container. For the chemical modification, 30 g of
CW samples was passed through a sieve of mesh size
between 18 and 25 (0.833 mm of particle size) and was
added to 210 mL of 0.6 M citric acid and the solution
was mechanical stirred at 250 rpm and heated to 60 °C
for 2 h. Subsequently, while it was still possible stirring,
the temperature was increased to 70 °C until the liquid
solution was totally evaporated. Then, it was dried at
120 °C for 6 h, followed by a 1-h wash with 1 L of
distilled water at 60 °C under agitation at 200 rpm. This
washing process was carried out sometimes to remove
excess citric acid that could contain the surface of the
adsorbent until a colorless solution is obtained. The
adsorbent was recovered by filtration and to confirm
that the surface does not contain excess citric acid, it
must be verified that there was no precipitate when
10 mL of 0.1 M Pb(NO3)2 was mixed with 10 mL of
the colorless solution obtained after the multiple washes.
Finally, when the precipitate was not detected in the
washing solution, the adsorbent was dried at 100 °C
for 15 h and stored hermetically before its use. The study
conducted by Cerino-Córdova et al. (2013a, b) shows
that the chemical modification of CW with 0.6 M citric
acid is the most convenient given its improvement in its
adsorption capacity.
2.2 Characterization of Chemically Modified Coffee
Waste
With the intention of identifying the functional groups at
the surface of the adsorbent, an infrared spectrum was
Page 3 of 14 73
performed using a Fourier transform infrared (FTIR)
spectrophotometer with attenuated total reflectance
(ATR). The number of functional groups and their equi-
librium constants of the modified coffee waste (MCW)
were determined experimentally by potentiometric titra-
tions according to the method proposed by Yun et al.
(2001). The pH values of point of zero charge (pHPZC)
of the CW and MCW were determined by a procedure
similar to that reported by Babić et al. (1999). In volu-
metric flasks containing a 0.1 M NaCl solution, different
volumes of 0.1 N HCl or 0.1 N NaOH were added to a
volume of 40 mL of solution. The prepared solutions
were added to 50-mL conical tubes containing 200 mg
of MCW. Finally, they were placed under agitation for
2 days at 200 rpm. The final pH of the solutions was
measured. The pHPZC was determined at the pH value
where the potentiometric titration curve has a plateau.
2.3 Extractable Calcium Content
Extractable calcium was determined according to the
Analytical Methods for Atomic Absorption Spectrosco-
py AY-1. Samples of 5.0 g of dried MCW with a particle
size between 0.701 and 0.833 mm were placed in an
Erlenmeyer flask with 20 mL of extracting solution
(0.05 N HCl + 0.025 N H2SO4). After 15 min of
mechanically stirring, the samples were filtered, and
the solution was placed in 50 mL volumetric containers
and diluted to 50 mL with extraction solution. The
solution obtained was analyzed by atomic absorption
spectrophotometry (AAS) in a Thermo-Scientific
SOLAAR 989 equipment flame atomic absorption
(The Perkin-Elmer Corporation 1996).
2.4 Adsorption Experiments
The adsorption isotherms of Cu(II) and Pb(II) were
carried out in 50-mL flasks containing 40 mL of metal
solutions with different initial concentration. Forty mil-
ligrams of MCW was added to 40 mL of a solution at
pH 5 containing Pb(II) and/or Cu(II). Flasks were stirred
in an orbital shaker at 200 rpm and 30 °C for 5 days to
ensure that adsorption equilibrium was reached (Cerino-
Córdova et al. 2013a, 2013b). According to the specia-
tion diagrams for both, Cu(II) an Pb(II) (Supplementary
material A), during adsorption experiments, pH was
kept constant at 5 by addition of 0.1 N NaOH because,
at pH greater than 5.5, both metal ions precipitate even
at low concentrations. The initial concentration of metal
 73 Page 4 of 14
varied from 0.2 to 2 meq/L for individual Cu(II) and
Pb(II) adsorption and for the binary adsorption system.
The adsorption experiments were conducted by
duplicate.
The concentrations of Cu(II) and Pb(II) in solution
were determined by AAS at a wavelength of 217 and
324.8 nm for Pb(II) and Cu(II), respectively. The quan-
titative determination of potentially toxic metals in
aqueous solution was carried out using a calibration
curve at different concentrations: 0.0315–0.1575 meq/
L for Cu(II) and 0.0096–0.0965 meq/L for Pb(II). Based
on these measurements, the metal adsorption capacity
was calculated using Eq. (1).
V ðC o −C e Þ
qe ¼ ð1Þ
m hydrogen and calcium ions in meq/L, respectively.
where V is the solution volume (L), Co and Ce are the
initial and final metal concentrations (meq/L), and m is
adsorbent mass (g).
2.5 Exchangeable Cation Determination
The AY-2 method of the Analytical Methods for
Atomic Absorption Spectroscopy was used to deter-
mine the concentration of exchangeable nutrient ele-
ments in the adsorbent and quantify the exchangeable
calcium, magnesium, sodium, and potassium ions in
the MCW.
The MCW samples were dried and sieved for a
particle size of 0.701–0.833 mm, then a sample of
2.5 g was placed in a 125-mL Erlenmeyer flask with
25 mL of 1 N CH3COONH4 at pH 7.0. The MCW
samples were shaken and filtered, and the solution was
analyzed by AAS.
2.6 Proposed Model for Binary Adsorption
at Equilibrium
The experimental data of equilibrium can be adjusted to
mathematical models that relate the capacity of adsorp-
tion and the concentration in the equilibrium. The ad-
sorption equilibrium can be modeled considering an ion
exchange between the cations present in the modified
solid coffee waste, usually Ca2+ and H+ cations, and the
ions present in the aqueous phase (Cu(II) and Pb(II)) for
the binary system.
Water Air Soil Pollut (2019) 230:73
The reactions are represented as follows:
M2þ þ 2HB↔MB2 þ 2Hþ ð2Þ
M2þ þ CaB2 ↔MB2 þ Ca2þ ð3Þ
where M is Cu or Pb, HB represents the protonated
adsorption sites, B represents the adsorption sites (hy-
droxylic, carboxylic) and CaB2 represents the adsorp-
tion sites neutralized with calcium ions.
Eq. (4) gives the total normality:
C o ¼ C Cu þ C Pb þ C H þ C Ca ð4Þ
where C° is the total normality in meq/L, CCu and CPb
are the concentrations of the Cu(II) and Pb(II) metal ions
in meq/L, and CH and CCa are the concentrations of
Since the adsorption sites are occupied by the ions
initially retained by the MCW, the number of active
sites is the sum of the ion concentrations in the solid
phase, represented by Eq. (5):
Q ¼ qCu þ qPb þ qH þ qCa ð5Þ
where Q is the number of active sites in meq/g, qCu, qPb,
qH, and qCa represent the amount of potentially toxic
metal ions Cu(II) and Pb(II), hydrogen, and calcium, in
meq/g, respectively. The equivalent fraction of a com-
ponent in the liquid phase xi is the ratio of its concen-
tration in the liquid phase (Ci in meq/L) and the normal-
ity of the liquid solution (C°):
Ci
xi ¼ ð6Þ
Co
In a similar manner, the solid phase fraction yi is
obtained from the ratio of the concentration in the solid
phase (qi in meq/g) and the concentration of the solution
in the solid phase (Q in meq/q):
qi
yi ¼ ð7Þ
Q
The sum of the equivalent fractions in each phase is
equal to 1:
xCu þ xPb þ xH þ xCa ¼ 1 ð8Þ
yCu þ yPb þ yH þ yCa ¼ 1 ð9Þ
where xCu, xPb, xH, and xCa represent the potentially
toxic metal, hydrogen, and calcium ion fractions in
Water Air Soil Pollut (2019) 230:73 Page 5 of 14 73

liquid phase, respectively, while yCu, yPb, yH, and yCa SQE
R2 ¼ 1− ð16Þ
represent fractions of potentially toxic metal ion, hydro- Ct
gen, and calcium on the solid phase. The separation
factor represents the relative selectivity of one species 1 m exp
qexp
i − ∑q
over the other and is defined as follows: m m i¼1 i
Ct ¼ ∑ exp ð17Þ
y xH i¼1 qi
αM
H ¼ M ð10Þ
xM yH
Rc2 was used to compare the results obtained between
the different models studied. In the analysis, Rc2 is used
yM xCa
Ca ¼
αM ð11Þ instead of R2 since it considers the number of free pa-
xM yCa rameters, which is necessary to compare various models
where αM H and αCa represent the separation factors be-
M with different degrees of freedom (Joshi et al. 2006).
tween the metal ion (Cu(II) or Pb(II)) and the exchange-
able ions (Ca2+ and H+). The separation factor has been
used by some authors to describe the equilibrium rela- 3 Results and Discussion
tionships in the multicomponent ion exchange (da Silva
et al. 2015; Das Graças Nunes Matos et al. 2009; 3.1 Characterization of the Unmodified and Modified
Sulaymon et al. 2013). Combining Eqs. (8)–(11) gives Coffee Waste
the ion exchange equilibrium models proposed in this
study for the multicomponent adsorption of Cu(II) or An infrared spectrum of the unmodified and modified
Pb(II) (Eq. (12)) and in the normalized matter (Eq. (13)): coffee waste was performed to identify the functional
x groups before and after the modification (Fig. 1). Ab-
yM1 ¼

M2 Ca  M 1
H 
1−αCa
M1 x M 1 þ α M1 −α M1 x M2 þ αM1 −αM1 xH þ αM1 xCa
Ca Ca sorption bands corresponding to the stretching of hy-
ð12Þ droxyl groups (O–H) were found at 3350 cm−1, aliphatic
groups (C–H) at 2930 cm−1; and the stretching of car-
qM1 ¼

M2 Ca 
Q C M1

H  boxylic groups (C=O) at 1742 cm−1 as well as the
M1 C M1 þ αM1 −αM1 C M2 þ αM1 −αM1 C H þ αM1 C Ca
1−αCa stretching of the (C=C) at 1640 cm−1; the methyl groups
Ca Ca

ð13Þ (CH2) at 1460 cm−1 and (CH3) at 1375 cm−1; and

carbonyl groups (C–O) in the range between 1300 and
The model parameters were evaluated using the gen-
1100 cm−1 similar to those reported by Liu et al. (2015).
eralized reduced gradient (GRG) non-linear regression
The increase in the absorption band intensity of the
method using an optimization routine to minimize the
carboxyl groups after the chemical modification is at-
sum of the quadratic error (SQE) via the solver tool of
tributed to the esterification reactions of the hydroxyl
Microsoft Excel®. The SQE was calculated by the
groups present on the surface of the CW and the citric
following equation:
acid generating more carboxylic groups on the surface
!2 of the material (Wartelle and Marshall 2000; Zhou et al.
n qexp −qcal
SQE ¼ ∑ ð14Þ 2015; Zhu et al. 2008). Carboxylic groups have been
i¼1 qexp
reported as contributing most to the adsorption of po-
where qexp is the experimental adsorption capacity and tentially toxic metals onto coffee waste (Cerino-
qcal is the calculated adsorption capacity. Córdova et al. 2013a, b).
Model accuracy was tested with the coefficient of The pHPZC value of the MCW was obtained experi-
regression (Rc2) with degrees of freedom df = m − k, mentally and is illustrated in Fig. 2. The pHPZC of the
where m is the number of sample points and k is the MCW was 2.97 which corresponds to the pH when the
number of model parameters (Montgomery 1987). final pH value is equal to the initial pH. This pHPZC

 value is similar to that reported by Cerino-Córdova et al.
2
2 k 1−R (2013a, b), which was 2.8. At a pH value above the
Rc ¼ R −
2
ð15Þ
df −1 pHPZC, the surface charge of the adsorbent is negative
where which is favorable for the adsorption of cationic species.
 73 Page 6 of 14 Water Air Soil Pollut (2019) 230:73

Fig. 1 IR spectrum of the solid residue of natural coffee residual (CM) and modified with citric acid (MCW)

Figure 3 shows the experimental data obtained by the
potentiometric titration of MCW. Each point of inflec-
tion represents a different functional group at the surface
of the adsorbent; thus, for each inflection point, a model
parameter must be considered.
The number of functional groups and pKa values were
calculated by non-linear regression. The values obtained
are shown in Table 1. The number of total acid sites of the
MCW obtained by potentiometric titrations was
5.26 mmol/g. During the modification, oxygen groups

Fig. 2 Determination of the point

of zero charge of the MCW
Water Air Soil Pollut (2019) 230:73 Page 7 of 14 73

Fig. 3 Potentiometric titration of the MCW

are introduced to the surface of the CW; these groups are capacity, which is 0.169 meq Cu/100 g of MCW. This
mainly carboxylic since the pKa values were approxi- capacity is found by dividing the concentration of cal-
mately 4 and 6. Some researchers reported pKa values cium in ppm by 10 times its equivalent weight. These
around 4 and 6 for carboxylic groups and 9.5 to 10.5 for results suggest a possible exchange that could be taking
hydroxyl groups (Webb 1987). The results indicate that place between the potentially toxic metals and the cal-
the surface of the modified coffee contains carboxylic cium content on the surface of the MCW. Thus, the
groups, as well as hydroxyls, which agree with the results analytical determination of the concentration of the ex-
obtained by infrared spectrophotometry analysis. changeable cation was carried out.
The concentrations of the exchangeable cations (i.e.,
3.1.1 Determination of Extractable Calcium Ca, K, Mg, and Na) in the MCW were 187, 66, 61, and
and Exchangeable Cation 51 nmol/g for Ca, Mg, Na, and K, respectively. Calcium
is the most abundant elements in the MCW. The trends
According to the concentration of extractable calcium of for the exchangeable cation in the MCW were as fol-
33.38 ppm, it was possible to calculate its exchange lows: Ca > Mg > Na > K, similar to the trends of the
major constituents of spent coffee grounds reported for
Table 1 Functional groups of the MCW (b, mmol/g) and pKa Pujol et al. (2013), Ca > Na > Fe > K.
Functional One parameter Two parameters Three parameters
groups model model model
3.2 Adsorption Isotherm of Cu(II) and Pb(II)
b1 3.61 2.22 1.03 on Modified Coffee Waste
pKa1 6.21 5.10 3.94
b2 – 2.67 1.63 The adsorption equilibrium studies shown in Figs. 4 and 5
pKa2 – 9.78 6.29 were carried out to obtain Cu(II) and Pb(II) adsorption
b3 – – 2.60 isotherms with MCW. The isotherms were modeled
pKa3 – – 10.19
using the Langmuir (Langmuir 1918), Freundlich
R2 0.943 0.983 0.992
(Freundlich 1927), and ion exchange models. In both
figures, favorable equilibria isotherms are presented,
 73 Page 8 of 14 Water Air Soil Pollut (2019) 230:73

Fig. 4 Adsorption isotherm of

Cu(II) on coffee residues
modified with 0.6 M citric acid at
30 °C and pH 5. The lines
represent the Langmuir,
Freundlich, and ion exchange
isotherms. The length between
both small diamonds represents
the standard deviation of the
duplicate measurements

since they have a convex behavior and a plateau can be
observed around 1.4 and 1.2 meq/g for Cu(II) and Pb(II)
adsorption, respectively. Nevertheless, Langmuir’s and
Freundlich’s models do not consider the fact that metal
ion adsorption is largely an ion exchange phenomenon.
They do not allow the prediction of the remaining bind-
ing of those ions (e.g., protons and/or calcium) that were
initially loaded onto the surface adsorbent, and neither do
they incorporate the concentration of the exchanged
The parameters associated with the adsorption iso-
therms of Cu(II) and Pb(II) and their coefficient of
regression are shown in Table 2. The ion exchange
model satisfactorily predicts the adsorption isotherms
of the divalent metal ions studied according to their
coefficient of regression.
Conforming to the ion exchange model, when com-
paring the separation factors of each metal, a general
tendency is observed αH M =αM ≫1, indicating that the met-
Ca

species (e.g., protons) as a parameter (Schiewer and al exchanges a proton more easily than a calcium ion.
Volesky 1995). This result is in accordance with the physicochemical

Fig. 5 Adsorption isotherm of

Pb(II) on coffee residues modified
with 0.6 M citric acid at 30 °C and
pH 5. The lines represent the
Langmuir, Freundlich, and ion
exchange isotherms. The length
between both small triangles
represents the standard deviation
of the duplicate measurements
Water Air Soil Pollut (2019) 230:73 Page 9 of 14 73

Table 2 Estimated parameters of the Langmuir, Freundlich, and ion exchange isotherms using the experimental data of Cu(II) and Pb(II)
adsorption on solid residues of coffee modified with 0.6 M citric acid

Ion The Langmuir The Freundlich Ion exchange

Cu(II) qmax (meq/g) 1.46 ± 0.59 K (meq1–1/n/g L–1/n) 1.41 ± 0.45 αCaCu 3.09 × 10−7
αHCu 8.65 ± 0.60
b (meq/L) 23.11 ± 0.60 n 2.44 ± 0.67 qmax (meq/g) 1.46 ± 0.59
Rc2 0.996 Rc2 0.975 Rc2 0.996
Pb(II) qmax (meq/g) 1.18 ± 0.63 K (meq1–1/n/g–L–1/n) 1.16 ± 0.42 αCaPb 1.09 × 10−12
αHPb 2.98 ± 0.75
b (meq/L) 67.16 ± 0.46 n 4.02 ± 0.66 qmax (meq/g) 1.18 ± 0.33
Rc2 0.994 Rc2 0.907 Rc2 0.994

characterization that indicates that the concentration of
protons is much higher than calcium. This behavior is a
result of the chemical modification of the material, since
it is possible that during the acid treatment, the calcium
ions was lixiviated, and the protons were increased due to
the insertion of carboxylic groups.
3.3 Competitive Adsorption Isotherm of Cu(II)
and Pb(II) on Modified Coffee Residues
The adsorption equilibrium studies shown in
Figs. 6, 7 and 8 were carried out to obtain competitive
adsorption isotherms of Cu(II) and Pb(II) onto MCW.

Fig. 6 Competitive ion exchange proposed model adsorption isotherm of Cu(II) with Pb(II) on MCW with 0.6 M citric acid at 30 °C and pH 5
 73 Page 10 of 14
Fig. 7 The proposed competitive ion exchange model adsorption isotherm of Pb(II) with Cu(II) on MCW with 0.6 M citric acid at 30 °C and pH 5
The separation factors in the ion exchange model
for the two metal ions studied in individual adsorp-
tion indicate that the solid residue of modified coffee
has a higher affinity for the metal ions and that it
exchanges protons almost exclusively since the con-
centration of the exchangeable cations analyzed was
very low.
The proposed competitive ion exchange model
considering the exchange between metal ions and
protons is shown in Eq. (12).
The regression coefficients from the models
studied for the competitive adsorption isotherms
of Cu(II) and Pb(II) are presented in Table 3.
The ion exchange model satisfactorily predicts
the adsorption isotherms of the divalent metal
ions studied according to their regression
coefficients.
Water Air Soil Pollut (2019) 230:73
The ion exchange model separation factors ratio of
the competitive adsorption allows to understand the
effect of a second adsorbate, since αH Pb =αPb ≫αCu =αCu
Cu H Pb
it is possible to elucidate that the adsorption capacity of
copper is diminished due to the presence of lead (Fig. 8).
This could be explained by the difference in the hydrat-
ed radii of both metals; the hydrated radius of any ion is
directly proportional to its charge (+ 2) and inversely
proportional to its ionic radius (0.69 and 1.2 Å for Cu(II)
and Pb(II), respectively). According to the ion exchange
theory, in a dilute aqueous phase containing exchange-
able ions, the ions with a smaller hydrated radius are
preferred because they reduce the swelling pressure of
the adsorbent and are more tightly bound to the adsor-
bent (Crittenden and Montgomery Watson Harza (Firm)
2012). The hydrated radius of Pb(II) (1.66 Å) is less than
that of Cu(II) (2.89 Å) which could explain the major
affinity of MCW for lead ions than the copper ions.
Water Air Soil Pollut (2019) 230:73 Page 11 of 14 73

Fig. 8 The proposed competitive ion exchange model adsorption isotherms on MCW with 0.6 M citric acid at 30 °C and pH 5. Blue surface
with lines is the model for lead and red grid surface for copper (Waterloo Maple Inc. 2014)

3.4 Comparison with Other Materials
The adsorption capacities of the modified coffee
waste for the removal of Cu(II) and Pb(II) at satura-
tion have been compared with those reported in the
literature for other adsorbents and the values for the
individual and competitive adsorption are shown in
Tables 4 and 5. The maximum individual adsorption
capacities of Cu(II) and Pb(II) were 1.46 and
1.18 meq/g, respectively, and 1.43 meq/g for Cu(II)
with Pb(II) and 1.24 meq/g for Pb(II) with Cu(II) for a
binary mixture. These individual adsorption capaci-
ties were 9.8 and 6.7 times greater than those obtained
with granular activated carbon (An 2001).

Table 3 Estimated parameters of

the competitive ion exchange Ion exchange parameters
isotherms using the experimental
data of Cu(II) with Pb(II) and Cu(II) αCuPb 2.51 ± 0.38 Pb(II) αPbCu 0.11 ± 0.38
Pb(II) with Cu(II) adsorption on αCuH 7.66 ± 0.36 αPbH 5.82 ± 0.31
solid residues of coffee modified
qmax (meq/g) 1.43 ± 0.42 qmax (meq/g) 1.24 ± 0.36
with 0.6 M citric acid
Rc2 0.982 Rc2 0.981
 73 Page 12 of 14 Water Air Soil Pollut (2019) 230:73

Table 4 Comparison of the

maximum individual adsorption Adsorbent Cu(II) Pb(II) pH Reference
capacity of different adsorbents
(meq/g) Amberlite 200 2.80 3.40 4.5–5 Vaughan et al. (2001)
Amberlite IRC-718 4.00 2.80 Vaughan et al. (2001)
Corncobs 0.24 0.08 Vaughan et al. (2001)
Granular activated carbon 0.16 0.16 5 An (2001)
Activated carbon powder 0.14 0.26 An (2001)
Roasted coffee beans 0.06 – 5.5 Minamisawa et al. (2004)
Coffee bean 0.24 – 6 Oliveira L.S. et al. (2008)
Spent coffee ground 0.44 0.48 4.5 Dávila-Guzmán et al. (2013),
Dávila-Guzmán (2016)
MCW 1.46 1.18 5 This research

Even though the adsorption capacities of Cu(II) and The physicochemical characterization of the
Pb(II) were 1.9 and 2.7 times lower than the reported MCW showed that this material has an acidic nature,
capacities for ion exchange resins (Vaughan et al. 2001), with a pHPZC of 2.97 and a preponderance of carbox-
the cost of these resins (63.5 USD/kg Amberlite® yl and hydroxyl type sites, which is in accordance
IR120 (BProduct Name Amberlite® IR120 hydrogen with the bio-polymeric nature of the material and the
from | Sigma-Aldrich^ n.d.)) is a disadvantage for their functionalization performed.
use in wastewater treatment compared to the cost of Experiments revealed that mainly the protons
producing 1 kg of MCW which is 10 dollars for the present in the carboxyl groups and not the micronu-
citric acid used (80.7 g) plus 2 dollars required for trient ions of the adsorbent structure are exchanged
electricity, water, etc., which means that it is more than with the metal ions in aqueous solution, thereby
5 times more economical. confirming that the main adsorption mechanism of
Pb(II) and Cu(II) on the MCW is ion exchange.
Likewise, the quantification of the exchangeable ions
unveiled that the order of exchange is as follows:
4 Conclusions H+ > Ca+2 > Mg+2 > Na+ > K+.
The results showed that the main exchangeable ion is
The coffee waste modified with 0.6 M citric acid the proton, in both individual and binary adsorptions.
(MCW) has a high removal capacity of Pb(II) and The separation coefficients corroborated the experimen-
Cu(II) from aqueous solutions in both individual and tal data and the regression coefficient indicated that the
binary systems. The maximum individual adsorption mathematical model accurately predicted the experi-
capacities were 1.18 and 1.46 meq/g, respectively, mental data of the adsorption equilibrium.
for Pb(II) and Cu(II) and 1.24 and 1.43 meq/g, Ion exchange model has the same mathematical
respectively, for competitive adsorption at pH 5 structure as the Langmuir model. The results ob-
and 30 °C. served in Figs. 4 and 5 and the regression coefficients
obtained (Table 2) confirm the mathematical similar-
Table 5 Comparison of the maximum adsorption capacity of ity. The model proposed by ion exchange in this work
Cu(II) and Pb(II) in competitive isotherms (meq/g) is a phenomenological model that considers the sur-
face chemistry of the adsorbent interacting with the
Adsorbent Cu(II) Pb(II) pH Reference
liquid phase; the others are empirical to describe
Algae 1.3 1.3 5 Pagnanelli et al. (2002) liquid phase adsorption.
Peat 0.576 0.85 4.45 Fei and Bei (2007) The phenomenological modeling provides an
Cabbage waste 0.297 0.582 6 Hossain et al. (2014) idea to understand and quantify the adsorption pro-
cess for a single, binary, ternary or more compo-
MCW 1.43 1.24 5 This research
nent system.
Water Air Soil Pollut (2019) 230:73
Acknowledgments The authors would like to acknowledge the
Department of Chemistry, Facultad de Ciencias Químicas, UANL,
for the laboratory space
Funding Information The study was financially supported by
Facultad de Ciencias Químicas, UANL. A partial scholarship
support was also received from CONACYT (329590).
Compliance with Ethical Standards
Conflict of Interest The authors declare that they have no
conflict of interest.
Publisher’s Note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional
affiliations.
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