Journal of Molecular Liquids 215 (2016) 555–564

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Sorption of heavy metal ions from aqueous solution using acid-treated

avocado kernel seeds and its FTIR spectroscopy characterization
L.L. Díaz-Muñoz a, A. Bonilla-Petriciolet a,⁎, H.E. Reynel-Ávila a,b, D.I. Mendoza-Castillo a,b
a
Tecnológico Nacional de México, Instituto Tecnológico de Aguascalientes, Aguascalientes, 20256, México
b
CONACYT, Cátedras Jóvenes Investigadores, D.F., 03940, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: This study reports the modification of surface chemistry of the avocado kernel seeds (i.e., Persea americana
Received 28 September 2015 biomass) using both organic and mineral acids and their application in the heavy metal removal from aqueous
Accepted 6 January 2016 solutions. The best conditions for the chemical treatment of this biomass using sulfuric, citric and tartaric acids
Available online 26 January 2016
have been identified using Taguchi experimental designs. The best acid-treated avocado seeds were used
in the sorption of heavy metal ions: Cd2+, Cu2+, Ni2+, Pb2+ and Zn2+ from aqueous solutions. Kinetic and
Keywords:
Heavy metals
equilibrium parameters of heavy metal sorption were determined. FTIR characterization of the modified avocado
Sorption kernel seeds with tested acids was performed for determining the impact of chemical treatment on the surface
Persea americana biomass modification and for identifying the functional groups involved in the metal uptake. Results showed that metal
FTIR characterization uptakes of acid-treated biomass can be increased up to 600%. In particular, citric and sulfuric acids are the
most effective chemical agents for improving the metal sorption properties of avocado kernel seeds. Maximum
sorption capacities of acid-treated avocado kernels ranged from 3.3 to 21.8 mg/g where the best removal
performance was obtained for Pb2+ ions.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction selectivity [10,11]. Different authors have reported experimental proto-

Wastes obtained from lignocellulosic biomasses can be used as sor-
bents in the control of water pollution. Lignocellulosic materials repre-
sent an emerging and attractive alternative to traditional adsorbents/
sorbents for heavy metal removal from aqueous solutions due to their
physicochemical properties, chemical stability, high reactivity besides
their abundance in nature and low cost [1–3]. A large variety of plants,
crops, fruits, agricultural and forest wastes have been applied in the re-
moval of these relevant water pollutants [1–8].
The affinity between biomass surface and metallic ions is paramount
in water treatment since raw lignocellulosic wastes may not be able to
efficiently remove these pollutants. Metal uptakes of these raw mate-
rials usually range from 1 to 10 mg/g depending on the metallic ion
and the operating conditions [1,2]. Sorption properties of lignocellulosic
biomasses are mainly determined by the chemical nature of its surface
(i.e., functional groups). The surface properties can be changed with dif-
ferent chemical treatments, which usually improve sorbent perfor-
mance for metal uptake via the introduction of new functional groups
[2,4,9]. The chemical modification of lignocellulosic biomasses may en-
hance their mechanical and sorption properties including the removal
⁎ Corresponding author.
E-mail address: petriciolet@hotmail.com (A. Bonilla-Petriciolet).
cols for the chemical modification of biomass surface chemistry giving
emphasis in the heavy metal removal from aqueous solutions [4,6,8,
10–14]. Literature indicates that metal uptakes of treated biomasses
may increase in orders of magnitude depending on the chemical agent
and operating conditions [2,10]. It appears that the improvements on
sorption properties of lignocellulosic biomasses are higher using acid
treatments than those obtained with other chemical agents [4,5,10,12,
13]. However, the major challenge in the biomass chemical treatment
involves the identification of the most effective modification procedure
and the tailoring of the biomass surface chemistry for the selective re-
moval of metallic ions. Note that a thorough knowledge of biomass sur-
face chemistry enables the preparation of sorbents with appropriate
characteristics for water treatment.
This article reports the modification of surface chemistry of the avo-
cado kernel seeds (i.e., Persea americana biomass) using both organic
and mineral acids and their application in the heavy metal removal
from aqueous solutions. Avocado wastes have emerged as a promising
low-cost feedstock for the preparation of novel materials for water pol-
lution control [15–19]. These lignocellulosic wastes contain chemical
functional groups that may interact with heavy metal ions in aqueous
solutions [15,17]. However, studies regarding the surface modification
of this biomass with organic and mineral acids for improving the
heavy metal uptakes and its FTIR spectroscopy characterization are
scarce. Therefore, in this study, the best conditions for the chemical
treatment of this biomass using sulfuric, citric and tartaric acids have

http://dx.doi.org/10.1016/j.molliq.2016.01.022
0167-7322/© 2016 Elsevier B.V. All rights reserved.
 556
Table 1
Taguchi experimental design used for the acid treatment of avocado kernel seeds and its results in the heavy metal removal from aqueous solutions.

Acid treatment Thermal treatment Heavy metal uptake (mg/g) for

Pb2+ Cd2+ Ni2+ Zn2+ Cu2+

Biomass sample Concentration, M Biomass/acid ratio, g/mL Temperature, °C Time, h
AKTA AKCA AKSA AKTA AKCA AKSA AKTA AKCA AKSA AKTA AKCA AKSA AKTA AKCA AKSA

1 0.5 1/25 60 1 2.81 3.20 3.57 1.61 1.48 1.57 6.76 1.46 1.77 0.19 0.83 1.67 3.23 2.00 2.15
2 0.5 1/10 90 2 2.83 3.27 3.26 1.49 2.21 1.13 5.70 1.79 2.72 1.37 0.96 1.07 2.82 2.22 2.26
3 0.5 1/15 120 4 11.56 14.04 5.04 4.24 4.75 1.31 4.63 3.59 1.68 2.85 2.93 1.36 5.68 7.41 1.24
4 0.5 1/20 150 8 16.76 19.79 16.03 5.98 6.23 3.03 7.50 5.19 1.96 3.37 4.21 1.79 7.72 9.15 2.50
5 1 1/25 90 4 9.21 8.95 4.40 3.99 2.97 1.18 3.19 4.07 2.96 2.72 1.32 0.85 3.54 5.43 2.25
6 1 1/10 60 8 4.04 6.89 4.03 2.16 2.53 0.93 5.04 2.66 2.45 0.54 1.47 0.79 3.38 4.00 2.75
7 1 1/15 150 1 4.14 3.27 4.25 0.89 1.05 1.18 1.50 1.75 2.22 0.35 0.76 0.79 2.29 2.19 1.79
8 1 1/20 120 2 6.85 4.16 4.44 3.28 1.16 1.04 3.39 1.09 1.69 2.92 0.98 0.76 3.23 2.88 1.93
9 1.5 1/25 120 8 14.43 16.71 21.79 4.24 5.10 10.28 4.79 7.09 5.72 3.41 3.92 4.52 4.21 8.69 8.04

L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564

10 1.5 1/10 150 4 16.61 21.24 15.12 5.93 8.58 4.68 6.68 15.02 3.15 2.82 4.30 2.78 7.11 10.89 4.83
11 1.5 1/15 60 2 3.16 3.48 3.56 1.26 1.55 1.43 3.38 1.05 2.22 0.52 0.55 1.41 0.48 2.31 2.63
12 1.5 1/20 90 1 2.98 3.26 3.60 0.68 0.29 0.99 4.17 3.37 2.64 0.18 1.13 0.96 2.51 2.18 3.40
13 2 1/25 150 2 8.89 8.47 7.53 1.85 2.24 2.62 3.16 1.02 2.51 2.24 1.21 1.50 3.48 4.36 2.80
14 2 1/10 120 1 3.88 3.79 3.74 1.60 1.77 1.07 1.27 2.70 0.97 0.93 0.77 0.74 2.39 2.49 1.93
15 2 1/15 90 8 14.68 12.72 12.88 5.89 3.18 1.99 4.53 5.63 3.13 3.03 2.34 1.24 7.10 6.88 3.08
16 2 1/20 60 4 4.32 4.99 3.95 2.08 1.79 1.42 1.20 2.83 2.25 1.02 1.01 0.66 1.35 2.82 2.60
from water.
sorption properties of emerging biomasses used in heavy metal removal
of applying the proper chemical treatment for the improvement of the
volved in the metal uptake. Results of this study highlight the relevance
on the surface modification and for identifying the functional groups in-
acids was performed for determining the impact of chemical treatment
FTIR characterization of the modified avocado kernels with tested
where kinetic and equilibrium parameters have been determined.
such as Cd2 +, Cu2 +, Ni2 +, Pb2 + and Zn2 + from aqueous solutions
treated avocado seeds were used in the sorption of heavy metal ions
been identified using Taguchi experimental designs. The best acid-

from the Taguchi experimental design. a) Citric acid, b) tartaric acid and c) sulfuric acid.
Fig. 1. Change (%) in the metal uptake of acid-treated avocado kernel samples obtained
 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564 557

Fig. 2. Plots of mean S/N ratio for the variables used in the acid treatment of avocado kernel seeds. S/N ratio was calculated using Eqs. (2) and (3) and sorption results of Table 1.

2. Methodology used for the biomass modification where the tested variables were:
the acid concentration, the ratio of biomass mass to acid solution vol-
2.1. Biomass description and its chemical treatment using organic and min- ume used in the chemical treatment, the temperature and time for
eral acids the biomass thermal treatment. Note that these variables control
the reaction between the biomass and the acid and, consequently,
Avocado kernel seeds (AK) were used in this study. This biomass is they determine the physicochemical properties of the treated bio-
considered as a waste from food processing and it represents 10–13% mass. Four experimental levels were used for each variable and the
of the avocado fruit [19]. Specifically, AK were washed using boiling de- experimental design was applied for both organic and mineral
ionized water. Raw biomass samples were dried and sieved to obtain a acids. Metal uptakes of the acid-treated AK were used as the re-
mean particle diameter of 0.5 mm. These particles were used in both the sponse variable for the experimental design. Removal performance
acid treatment studies and the sorption of heavy metal ions. of acid-treated biomass samples was determined for Cd 2 + , Cu 2 + ,
Acid treatment of AK was performed according to the procedure re- Ni2+, Pb2+ and Zn2+ ions. Sorption experiments for the L16 experimen-
ported by Bojic et al. [5]. In particular, a specific biomass amount was tal designs were performed in batch reactors using a metal solution
added to an acid solution and the mixture biomass–acid was held at with an initial concentration of 250 mg/L at pH 5 and 30 °C. Solutions
40 °C for 2 h. The mixture was drained to separate the treated biomass were prepared using nitrate salts of analytical grade and deionized
and a thermal treatment consisting of the biomass heating was per- water. A biomass–solution ratio of 0.01 g/mL and 24 h of equilibrium
formed at a specific temperature (i.e., 60–150 °C) for a given time time were used in these removal experiments. Metal uptakes were
(i.e., 1–8 h). Organic and mineral acids were used in the chemical treat- calculated from sorption results using
ment of AK, which included tartaric acid (TA), citric acid (CA) and sulfu-

ric acid (SA). In particular, a L16 Taguchi experimental design was used C 0 −C f V metal
qM2þ ¼ ð1Þ
to identify the impact of the acid treatment on the metal uptakes of mbiomass
modified biomass and the best conditions for the surface chemistry
modification were determined. Table 1 shows the experimental design where qM2+ is the metal uptake of the biomass sample for metal M 2+
given in mg/g, C0 and Cf are the initial and final metal concentrations
in the solution used in the removal experiment given in mg/L, Vmetal is
Table 2 the volume of metal solution used in the experiment given in L and
Statistical analysis of the Taguchi experimental designs used for the acid treatment of av- mbiomass is the amount of biomass used in the sorption experiment
ocado kernel seeds.
given in g, respectively.
Statistical analysis for The best conditions for the AK acid treatment were identified using a
Citric acid Tartaric acid Sulfuric acid statistical analysis based on the signal to noise (S/N) ratio, which is de-
fined as
Variable used in biomass SSF σF SSF σF SSF σF
acid treatment " #!
1 X
nrep
1
Acid concentration 34.92 11.64 23.35 7.78 75.20 25.07 S=N ¼ −10 log ð2Þ
Biomass/acid ratio 8.84 2.95 11.10 3.70 23.68 7.89 nrep i¼1 x2i
Temperature of thermal
95.52 31.84 81.66 27.22 49.57 16.52
treatment where xi is the response obtained from the run i of the experimental de-
Time of thermal treatment 328.20 109.40 166.42 55.47 122.33 40.78
sign that is used to calculate the S/N ratio and nrep is the number of
558 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564

Table 3
Selected conditions of the acid treatment for improving the heavy metal uptakes of avocado kernel seeds and its physicochemical properties.

Conditions used for the acid modification of biomass surface Physicochemical properties

Functional groups,
Acid treatment Thermal treatment
Sorbent Yield, % pHpzc mmol/g

Concentration, M Biomass/acid ratio, g/mL Temperature, °C Time, h Acidic Basic

AKCA 1.5 1/10 150 4 100 2.32 3.21 1.21

AKTA 0.5 1/20 150 8 96.7 2.35 3.08 1.40
AKSA 1.5 1/25 120 8 57.2 2.32 2.95 1.45
Raw AK – – – – 5.8 2.36 1.92

replicates for this run (i.e., nrep = 2 for this study), respectively. The SS F
σF ¼ ð6Þ
analysis of S/N ratio was used to improve the metal uptakes of treated vF
biomasses. Based on the fact that the target was to enhance the removal
behavior of AK for all tested heavy metals, the S/N analysis was per- where ndat is the total number of experimental data, nFi is the number of
formed using the next response variable obtained from the sorption re- experimental runs under the level i, Fi is obtained from the sum of the
sults of L16 experimental design response variable for the experimental runs under the level i, Tt is the
sum of the response variable for all experimental runs, yi is the value
qTotal ¼ qCd2þ þ qCu2þ þ qNi2þ þ qPb2þ þ qZn2þ ð3Þ of the S/N ratio, SST is the total sum of squares, kF is the number of levels
of factor F (i.e., the variable analyzed in the biomass acid treatment),
where qTotal is given in mg/g and it was calculated for each biomass sam- vF is the degrees of freedom of factor F (i.e., kF − 1), σF is the variance
ple obtained from the experimental design. Therefore, the improvement for factor F and SSF is the sum of squares for factor F, respectively.
in the value of S/N ratio also implies better sorption properties of the This statistical analysis was performed for each acid used in the
acid-treated biomass for each metallic ion. The statistical analysis of ex- biomass surface modification. The best conditions of acid treatment
perimental designs was performed with Eqs. (2) and (3) and using the were identified for each acid solution where the objective was selecting
next expressions the operating conditions that increased the S/N ratio (i.e., the increment
of qTotal).
" # Kinetic and equilibrium sorption studies were performed for all
X
ndat
T 2t
SST ¼ y2i − ð4Þ heavy metal ions using the best acid-treated biomasses. Kinetic rates
i¼1
ndat were determined for all metallic ions using an initial concentration of
100 mg/L at 30 °C and pH 5. On the other hand, the metal sorption iso-
" !#
XkF
F 2i T 2t therms were obtained at 30 °C and pH 5 where the initial metal concen-
SS F ¼ − ð5Þ trations ranged from 20 to 250 mg/L and the equilibrium time was 24 h.
i¼1
n Fi ndat
All sorption experiments were performed in batch reactors using a

Fig. 3. SEM images of raw and acid-treated avocado kernel samples.

 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564
Fig. 4. a) Kinetics, b) intra-particle diffusion analysis and c) isotherms for the uptake of
heavy metals on raw avocado kernel seeds at pH 5 and 30 °C.
biomass–solution ratio of 0.01 g/mL and constant stirring of 150 rpm.
Metal uptake rates were calculated using the pseudo-second order
model and the isotherms were adjusted to the Sips equation. Note
that the pseudo-second order kinetic model has been reported as an ef-
fective approach for the analysis of the uptake of divalent cations [20],
while the Sips model was used for data correlation because both the
Langmuir and Freundlich isotherms did not provide satisfactory perfor-
mance for modeling the results of this study. On the other hand, the
intraparticle diffusion analysis was performed using the Weber–Morris
559
approach, which is based on the plot t0.5 − qt, and the intraparticle dif-
fusion rates were calculated. Finally, the removal performance of the
best acid-treated AK was compared with that obtained for raw AK.
2.2. Physicochemical characterization of raw and acid-treated avocado
kernel seeds
The acidity, basicity and pH of zero charge (pHpzc) of both raw and
acid-treated AK were determined using the methodology reported by
Faria et al. [21]. Specifically, the total basic sites were obtained by
mixing 0.2 g of each biomass sample with 25 mL of HCl solution
0.025 M. The biomass–solution suspension was maintained under con-
tinuous stirring for 48 h at 30 °C. The suspension was decanted and the
remaining solution was titrated with NaOH 0.025 M. The total acidic
sites for all biomass samples were obtained in a similar way but using
NaOH 0.025 M for the suspension and the titration solution was HCl
0.025 M. In the case of pHpzc, NaCl solutions with different concentra-
tions (i.e., 0.01, 0.1 and 1.0 M) were prepared and the initial pH was ad-
justed to 4–7 for raw AK and to 2–4 for acid-treated AK. In particular,
0.15 g of each biomass sample was mixed with the electrolyte solution
and the final pH (pHf) was recorded after 48 h of constant stirring at
30 °C. The difference between initial and final pH (i.e., ΔpH) was calcu-
lated and a plot of the initial pH versus ΔpH was used to identify the
pHpzc. Removal performance of both raw and acid-treated AK samples
was related to these physicochemical properties. FTIR spectra of raw
AK and acid-treated AK, with and without loaded heavy metals, were
determined using a Thermo Scientific Nicolet iS10 FTIR spectrophotom-
eter. These spectra were recorded in the region 4000 to 600 cm−1 with
a resolution of 4 cm−1 and 32 scans. The raw AK and those samples
treated with citric and tartaric acids were measured with the ATR tech-
nique (Attenuated Total Reflectance) and the sulfuric acid-treated AK
samples were dispersed in KBr reactive to be measured as pellets. Final-
ly, the morphology of both raw and acid-treated AK samples was ob-
served using scanning electron microscopy. SEM micrographs were
obtained with secondary electrons using a JEOL JSM-5900 LV micro-
scope operated at 10 kV. Prior to the analysis, all samples were mounted
in SEM cylinders using adhesive double sided carbon tape and then
coated with a thin layer of gold using a Denton Vacuum coater to ensure
their conductivity.
3. Results and discussion
3.1. Acid treatment of AK and its heavy metal removal performance
Table 1 shows the results of metal removal experiments using the
different samples of acid-treated biomasses that were obtained with
the conditions of the Taguchi experimental design. In particular, the
metal uptakes of biomasses treated with both organic and mineral
acids are reported in this table. Note that the nomenclature used for
the samples is AKTA for tartaric acid, AKCA for citric acid and AKSA for
sulfuric acid. Metal uptakes ranged from 0.18 to 16.8 for AKTA, 0.29 to
21.2 for AKCA and 0.66 to 21.8 mg/g for AKSA, respectively. As expected,
the uptake of treated-acid AK depended on both the acid treatment con-
ditions and the metallic ion. It is convenient to remark that all acids have
a significant impact on the sorption properties of the AK. For illustration,
Fig. 1 shows the change (given in %) of the metal uptakes of acid-treated
biomass samples, which have been calculated using the metal uptake of
the raw AK obtained at the same sorption conditions
!
2þ
M2þ
qM biomass −qraw biomass
Change in metal uptake ¼ treated
2þ
 100 ð7Þ
qM
raw biomass
Metal uptakes may increase up to 600% for treated biomasses but it
is clear that the proper selection of the acid treatment conditions is cru-
cial for improving the sorption properties of AK. Results also suggest
560 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564

Fig. 5. Sorption kinetics of heavy metals on the best acid-treated avocado kernel seeds. Experimental data obtained at 30 °C and pH 5.

that the identification of the best conditions to increase the metal up-
takes of AK using the sulfuric acid appears to be more challenging in
comparison with organic acids. In fact, for some conditions employed
Table 4
Kinetic rates for the sorption of heavy metals using the best acid-treated avocado seed in the chemical treatment, the acid-modified AK may show lower
kernels. metal uptakes than those obtained for raw AK. The biomass yields ob-
tained from these experimental designs are 67.5 ± 18.3 for AKCA,
Kinetic rates for the sorption of heavy metals
53.1 ± 19.3 for AKTA and 45.4 ± 18.0% for AKSA. These results also sug-
k2, g/mg h kp, mg/g h0.5 gest that the sulfuric acid treatment may cause significant changes on
2+ 2+ 2+ 2+ 2+
Biomass Pb Cd Ni Cu Zn Pb2+ Cd2+ Ni2+ Cu2+ Zn2+ the AK chemical structure.
AKCA 2.04 0.81 0.64 0.51 0.26 0.77 0.90 0.75 1.77 1.61 The tailoring of sorption properties of lignocellulosic sorbents is a
AKTA 0.49 0.72 0.48 1.07 0.20 3.34 1.62 1.42 0.66 1.37 difficult task and requires standardized experimental protocols to iden-
AKSA 0.29 0.09 0.82 0.54 0.08 2.59 3.21 0.86 1.32 0.73 tify those conditions that may enhance the pollutant uptakes. Herein, it
q2 k2 t
qt ¼ 1þqte where qt is the metal uptake (mg/g) at time t (h), qte is the estimated metal
is important to remark that the mechanism of metal binding on ligno-
te k2 t

uptake at the equilibrium (mg/g) and k2 is the metal sorption rate (g/mg h); qt =
cellulosic biomasses is a topic of great debate. In fact, the removal of
kpt0.5 +α where kp is the intra-particle diffusion rate constant (mg/g h0.5) and the value heavy metals using these sorbents could involve several mechanisms
of α indicates if the intraparticle diffusion is the sole rate-limiting step. such as chemisorption, complexation, ion exchange, quelation,
 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564 561

Fig. 6. Intraparticle diffusion analysis for the sorption of heavy metals on the best acid-treated avocado kernel seeds. Experimental data obtained at 30 °C and pH 5.

electrostatic interactions and physical entrapment in the inter- and
intra-structural network of the sorbent [4]. The presence of these re-
moval mechanisms is mainly related to the characteristics and proper-
ties of the biomass under study. The acid treatment can modify the
surface characteristics of AK by introducing, removing or masking
some functional groups or by exposing more binding sites [4]. But, de-
pending on the acid treatment conditions, it could cause unfavorable ef-
fects on the biomass surface due to crosslinking reactions of the natural
polymers contained in the lignocellulosic material and the possible col-
lapsing of active metal-binding sites, thus affecting the removal mecha-
nisms involved in the heavy metal sorption [9,12]. Therefore, the
reaction acid–biomass must be controlled via the selection of the best
treatment conditions to maximize the sorption properties. Similar find-
ings have been reported by other authors that have performed chemical
modification of lignocellulosic sorbents using acid solutions [4,9].
Plots of S/N ratio for the variables tested in the biomass acid treat-
ment are reported in Fig. 2 where the corresponding statistical analysis
of the experimental designs is given in Table 2. Results of S/N ratios con-
firmed that the acid treatment conditions have a significant effect on the
sorption properties of AK. Metal uptakes improved with respect to the
conditions of the biomass thermal treatment for both organic and min-
eral acids. For citric and tartaric acids, the biomass heating has a relevant
impact on the heavy metal uptakes. In the case of sulfuric acid, the tem-
perature of thermal treatment and the acid concentration appear to be
the most important variables for improving the sorption properties of
AKSA. The best treatment conditions for each acid were identified via
the maximization of the S/N ratio, which implies an improvement on
the metal uptakes of treated AK. Also, the yields of treated biomasses
were considered for determining these conditions. Table 3 contains
the suggested values for performing the AK treatment using both organ-
ic and mineral acids. The physicochemical properties of the best acid-
treated AK are also reported in this table including the raw AK. Overall,
the amount of acidic groups increased up to 36% for AK treated with or-
ganic and mineral acids, while the pHpzc decreased in all cases (~2.3)
562 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564
Fig. 7. Isotherms for the sorption of heavy metal on the best acid-treated avocado kernel seeds. Experimental data obtained at 30 °C and pH 5. Sips model: qe ¼
and it was lower than those obtained for raw AK (~5.8). However, AKCA
showed the highest amount of acidic groups and the lowest pHpzc of all
sorbents. For illustration, Fig. 3 shows the SEM of raw and acid-treated
AK. Raw AK exhibited a rigid, rough and constricted surface. After acid
treatment, the biomass suffers morphological changes in its structure.
Results showed that the morphology of AKSA, AKCA and AKTA was ex-
tremely varied and different. In particular, the treatment with citric acid
unclogs the AK cavities favoring the development of enlarged openings
and degradation of the surface. Similar results have been reported by
Kim and Huber [22]. SEM images also showed the presence of numerous
randomly oriented cavities in AKSA sample. This acid-treated biomass
has heterogeneous, irregular and amorphous dispersed pits. These mor-
phological changes could be attributed to the partial destruction of cel-
lulose, hemicellulose and lignin induced by the sulfuric acid treatment
[23]. Finally, AKTA microstructure also showed pores with different
sizes and shapes. Note that these morphological changes on acid-
treated AK can contribute to the improvement of its sorption properties.
Kinetic rates for metal uptakes were determined for both raw and
the best acid-treated biomasses and results are reported in Figs. 4 and
1=n
qs as C e
1=n :
1þas C e
5, and Table 4. In particular, the sorption rates ranged from 0.08 to
2.04 g/mg h for treated AK where the highest rates have been obtained
for Pb2+ and Cu2+. Sorption rates are higher for AKCA and AKTA than
those obtained for AKSA (see Table 4). It is convenient to note that ki-
netic rates of raw AK ranged from 0.06 to 0.37 g/mg h and, consequent-
ly, the removal of heavy metal ions using treated-acid AK is faster due to
the increment of functional groups on the biomass surface. Kinetic re-
sults clearly indicated that 24 h are enough for reaching the sorption
equilibrium at tested experimental conditions using all biomasses. On
the other hand, the intraparticle diffusion analysis is reported in Figs.
4 and 6 for raw and acid-treated AK, respectively. Weber–Morris plots
for all heavy metals showed a multi-linearity behavior, which suggests
that several steps may be involved in the sorption mechanism of
heavy metal ions on both raw and acid-treated AK. These linear plots
have a sharp section that could be related to a predominant sorption
of the heavy metal ions on the external surface of AK samples. Lignocel-
lulosic wastes can be considered as non-porous sorbents with a low spe-
cific surface area (i.e., 53 m2/g determined with methylene blue) [15]
and, consequently, it is expected that the type and quantity of functional
 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564
Fig. 8. FTIR spectra of a) raw and acid-treated avocado kernel seeds, and b–f) acid-treated biomass loaded with heavy metals. Heavy metal ions: b) Cd2+, c) Cu2+, d) Ni2+, e) Pb2+, and
f) Zn2+.
groups of the biomass external surface play a crucial role for the removal
of heavy metal ions. In all cases, the intraparticle diffusion is presented
in the removal of tested heavy metals using all biomasses. However,
this diffusion is not the rate limiting step. Diffusion rates ranged from
0.30 to 0.72 for raw AK and from 0.66 to 3.34 mg/g h0.5 for acid-
treated AK, respectively.
Figs. 4 and 7 show the isotherms obtained for metal sorption using
AK samples. Maximum metal uptakes ranged from 2.5 to 5.6 mg/g for
raw AK and from 3.34 to 21.8 mg/g for acid-treated AK. The increment
on metal uptakes of AK after acid treatment ranged from 36 to 646%.
In particular, the sorption properties of treated AK increased significant-
ly for Ni2+ and Cu2+ ions. AKCA showed the maximum metal uptakes
for Pb2+, Ni2+ and Cu2+ ions, while AKSA showed the highest sorption
capacities for Cd2+ and Zn2+ ions (see Fig. 7). The order of metal sorp-
tion capacities for the acid-treated AK is:
AKCA: Pb2+ N Ni2+ N Cu2+ N Cd2+ N Zn2+
AKTA: Pb2+ N Cu2+ N Ni2+ N Cd2+ N Zn2+
AKSA: Pb2+ N Cd2+ N Cu2+ N Ni2+ N Zn2+
It is interesting to note that AK treated with organic acids showed al-
most the same trend for the maximum metal uptakes. In addition, all
563
acid-treated AK showed the higher sorption performance for Pb2 +
ions while the lowest uptakes were obtained for Zn2 + ions. Overall,
these sorption capacities are higher than those reported for other sor-
bents/adsorbents such as commercial activated carbons and other bio-
masses [11,24].
3.2. FTIR physicochemical characterization of raw and acid-treated AK
Lignocellulosic wastes are mainly composed of lignin, cellulose and
hemicellulose, which contain a variety of functional groups that can be
involved in the binding of heavy metal ions [4]. Therefore, the FTIR spec-
tra can be used as evidence of the introduction of new functional groups
in the surface of acid-treated AK. In particular, Fig. 8 shows the normal-
ized infrared spectra of the AK samples. In the region 3500–3000 cm−1,
spectra of raw and modified AK (Fig. 8a) show a strong band that ap-
pears with different intensity, which can be attributed to the OH
group from the intermolecular hydrogen bonds of phenols and alcohols
in lignin and cellulose [25–27]. The bands around 2900 and 1430 cm−1
represent the aliphatic stretching and bending vibrations, respectively
[23]. The band at 1619 cm−1 is assigned to C =O stretching vibration
of carboxylic group and structural vibrations of aromatic C=C bonds.
The vibration band at 1521 cm−1 corresponds to C = C of aromatic
rings of lignin [28]. Additionally, the vibration bands observed at 1361,
1200, 935, and 860 cm−1 can be related to the glycosidic linkages of cel-
lulose and hemicellulose where the peaks at 1360–1000 cm− 1 are
564 L.L. Díaz-Muñoz et al. / Journal of Molecular Liquids 215 (2016) 555–564
assigned to C–O stretching vibrations that denote acids, alcohols, phe-
nols, ethers and esters [23,25,27]. The band at 1024 cm−1 is related to
C–N deformation vibration of aliphatic amines [27]. The vibrations of
C–H bending can be observed at 935 cm−1 [23], while the peaks at
860–750 and 650 cm−1 involve vibrations associated to ring structures
[28,29].
After acid treatment, the biomasses present structural changes in
their FTIR spectra, see Fig. 8a. The band at 1521 cm− 1 is absent in
AKSA and decreased in AKCA samples, which suggests a reaction of de-
polymerization of aromatic ring of lignin that could lead to a lignin re-
moval [23,30]. Additionally, the band at 935 cm− 1 was also lost
during the treatment with citric acid and sulfuric acid and these results
confirm the structural degradation of the lignocellulosic material [23].
The bands in the near 3400–3300 cm−1 (OH groups); 1620, 1361 and
1150 cm−1 (C–O groups) and 1430 cm−1 (CH groups) decreased in in-
tensity and they shifted slightly. Reductions and shifts in FTIR peak po-
sitions can be related to condensation reactions and/or splitting of lignin
aliphatic, as well as the removal of part of cellulose and hemicellulose
[30–32]. The new absorption band around 1730 cm− 1 in AKTA and
AKCA samples can be associated to C = O stretching vibrations. This
band is related to the formation and increase of carbonyl groups via
the degradation of β-linkages by acid treatment [32]. Note that the bio-
mass acid treatment could expose some new groups due to structural
degradation [32]. It is important to remark that citric and sulfuric acids
showed a stronger effect in surface modification that those obtained
for tartaric acid.
After heavy metal sorption, some changes were observed in the FTIR
spectra of AK samples (see Fig. 8b–f). In raw AK, the peaks at 1619 and
1172 cm− 1 shifted slightly, while the peaks in the range 3400–
3300 cm− 1 shifted and the bands at 1730, 1635 and 1100 cm− 1 de-
creased in AKTA and AKCA samples. In AKSA samples, the bands at
3400–3300 cm−1 shifted and the vibration bands at 1730, 1350, 1100
and 1050 cm− 1 decreased. These bands are related to oxygenated
groups such as alcohols, ethers, esters, phenols and carboxylic acids
[23,25,27]. The changes in FTIR spectra could suggest that metal sorp-
tion leads to the oxidation of surface functional groups and a possible
complexation reaction between metals and those groups. A similar ob-
servation with lignocellulosic biomasses has been reported in other
studies, e.g., Bhaumik et al. [17]. In summary, these FTIR results are con-
sistent with the mechanisms proposed for the removal of heavy metal
ions using lignocellulosic biomasses [10,33,34], which could involve
the following reactions
2ð≡S–OHÞ þ M2þ →ð≡S–OÞ2 M þ 2Hþ ð11Þ
2ð≡S–COOHÞ þ M2þ →ð≡S–COOÞ2 M þ 2Hþ ð12Þ
2ð≡S–C6 H5 –OHÞ þ M2þ →ð≡S–C6 H5 –OÞ2 M þ 2Hþ ð13Þ
2+
where M corresponds to the heavy metal ion involved in the
removal process and S represents the biomass surface. Therefore, the
mechanism for the sorption of heavy metals using acid-treated AK
could be ion exchange and complexation processes where the interac-
tions with acidic groups (i.e., phenolic, carboxylic and hydroxyl groups)
of the biomass surface may be involved.
4. Conclusions
The acid treatment of avocado kernel seeds using both organic and
inorganic acids is an effective procedure for improving the sorption
properties of this biomass for the removal of heavy metal ions. However,
it is paramount to identify both the best treatment conditions and acid
type for enhancing its metal uptakes. In particular, the avocado kernel
seeds treated with citric and sulfuric acids showed the best metal up-
takes where their removal performance increased up to 600% due to
the surface modification. Metal sorption rates of acid-treated biomasses
were higher than those obtained for raw biomass. On the other hand,
the maximum metal uptakes ranged from 2.5 to 5.6 mg/g for raw avoca-
do kernel seeds and from 3.34 to 21.8 mg/g for acid-treated avocado
kernel seeds. Overall, acid-treated biomasses showed the higher metal
uptakes for Pb2 + ions and the lowest sorption capacities for Zn2 +
ions. FTIR characterization of the biomass samples showed that the
citric and sulfuric acids showed a stronger effect in surface modification
that those obtained for tartaric acid. The mechanism for the sorption of
heavy metals using acid-treated avocado kernel seeds could be ion ex-
change and complexation processes where the interactions with pheno-
lic, carboxylic and hydroxyl groups of the sorbent surface may be
involved.
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