Environ Sci Pollut Res (2014) 21:2054–2063

DOI 10.1007/s11356-013-2112-0

RESEARCH ARTICLE

Comparative study of adsorption of Pb(II) on native garlic peel

and mercerized garlic peel
Wei Liu & Yifeng Liu & Yaqi Tao & Youjie Yu &
Hongmei Jiang & Hongzhen Lian

Received: 22 April 2013 / Accepted: 29 August 2013 / Published online: 11 September 2013
# Springer-Verlag Berlin Heidelberg 2013

Abstract A comparative study using native garlic peel and Abbreviations

mercerized garlic peel as adsorbents for the removal of Pb2+
has been proposed. Under the optimized pH, contact time, and FAAS Flame atomic absorption spectrometry
adsorbent dosage, the adsorption capacity of garlic peel after EA Elemental analysis
mercerization was increased 2.1 times and up to 109.05 mg g−1. FT-IR Fourier transform infrared spectrometry
The equilibrium sorption data for both garlic peels fitted well SEM Scanning electron microscopy
with Langmuir adsorption isotherm, and the adsorbent–adsor- XPS X-ray photoelectron spectroscopy
bate kinetics followed pseudo-second-order model. These both
garlic peels were characterized by elemental analysis, Fourier
transform infrared spectrometry (FT-IR), and scanning electron
microscopy, and the results indicated that mercerized garlic Introduction
peel offers more little pores acted as adsorption sites than native
garlic peel and has lower polymerization and crystalline and As we all know, lead can be introduced into natural water from
more accessible functional hydroxyl groups, which resulted in a variety of sources such as metal processing, electroplating,
higher adsorption capacity than native garlic peel. The FT-IR electronics, and a wide range of chemical processing indus-
and X-ray photoelectron spectroscopy analyses of both garlic tries (Reddad et al. 2003). Lead entered into water can easily
peels before and after loaded with Pb2+ further illustrated that accumulate in human system through food chain and thus
lead was adsorbed on the through chelation between Pb2+ and cause damage to the kidney, liver, nervous, and reproductive
O atom existed on the surface of garlic peels. These results systems. Therefore, more attention is given to reduce the
described above showed that garlic peel after mercerization can concentration of lead in effluent wastewaters in view of envi-
be a more attractive adsorbent due to its faster sorption uptake ronmental protection as well as health problem.
and higher capacity. In recent years, numerous methods such as chemical pre-
cipitation (Matlock et al. 2001; Esalah et al. 2000; Mauchauffée
Keywords Native garlic peel . Mercerized garlic peel . et al. 2007), ion exchange (de Costa et al. 2010), liquid mem-
Adsorption . Pb brane extraction (Gherasim et al. 2011; Suren et al. 2012;
Rounaghi et al. 2013), electrode deposition (Sosa et al. 2000;
Hanewinkel et al. 2003; Martínez-Paredes et al. 2009), and
Responsible editor: Philippe Garrigues
adsorption (Yadanaparthi et al. 2009) have been applied to
W. Liu : Y. Liu : Y. Tao : Y. Yu : H. Jiang remove lead from aqueous solutions. When using chemical
College of Science, Nanjing Agricultural University, 1 Weigang,
precipitation method, different precipitants, for example, hy-
Nanjing 210095, China
droxides, sulfides, and phosphates, are needed and the chem-
H. Jiang (*) : H. Lian ical consumption is large, which may result in high costs
State Key Laboratory of Analytical Chemistry for Life Science, and secondary pollution. With respect to ion exchange, the
School of Chemistry & Chemical Engineering and Center of
removal rates is high; however, the adsorption capacity is
Materials Analysis, Nanjing University, 22 Hankou Road,
Nanjing 210093, China limited and needed to regenerate often. As regards liquid
e-mail: jianghongmei@njau.edu.cn membrane extraction, the serious problem is contamination
Environ Sci Pollut Res (2014) 21:2054–2063 2055

and stability of the membrane during the process of using. of Pb were investigated. Moreover, FT-IR and X-ray photo-
In regard to electrode deposition, the slow deposition rates electron spectroscopy (XPS) were used to study the adsorp-
of metal ion lead to long analytical time. Compared with the tion mechanism of the two materials. The Langmuir adsorp-
above methods, there has been growing concern about ad- tion isotherm and kinetics study were both proposed for the
sorption method because of its attractive advantages includ- present sorption research.
ing easy operation, availability of different adsorbents, and
cost-effectiveness.
In adsorption procedure, particular attention has been fo- Experimental
cused on a proper adsorbent to obtain high capacity and be
inexpensive and available at various locations around the Apparatus and instrumentation
world. To date, a variety of adsorbents, such as activated
carbon (Zhang et al. 2005; Pesavento et al. 2003; Ghaedi The lead concentrations were determined using Hitachi Z-
et al. 2008), mineral adsorbents (Inglezakis et al. 2007; 2000 atomic absorption spectrometer (Hitachi, Japan). A Pb
Chaari et al. 2008), inorganic material (Nata et al. 2010; hollow cathode lamp (Hitachi) operated at 6.5 mA was
White et al. 2009; Singh et al. 2011; Ngomsik et al. 2005), employed as the radiation source. Measurements were accom-
and biosorbents (Halttunen et al. 2007; Luo et al. 2006; Sarı plished in the integrated absorbance (peak area) mode at
et al. 2008), have been proposed to remove lead; however, 283.3 nm, with using a spectral band width of 1.3 nm.
there are still some problems in their applications, including The pH values were adjusted by a Mettler Toledo FE20 pH
the impurities in the adsorbents, slow adsorption kinetics, and meter (Mettler-Toledo, Shanghai, China) supplied with a com-
comparative large cost. In recent years, considerable efforts bined electrode. A KQ3200DE ultrasonic bath (Kunshan
have been put into agricultural wastes (Ngah et al. 2008) due Shumei Ultrasonic Instrument, Suzhou, China) was used to
to their local availability, technical feasibility, engineering speed up the adsorption process. A Model RJ-TDL-50A cen-
applicability, and cost-effectiveness. Up to now, a number of trifuge (Beijing Lab Centrifuge Co., Ltd., China) was applied
waste materials including sugarcane bagasse, sawdust, pecan to accelerate the phase separation. Native garlic peel and
nutshell, orange peel, grape bagasse, banana peel, and corn- mercerized garlic peel were characterized by TENSOR27
cobs (Gurgel et al. 2008; Rafatullah et al. 2009; Vaghetti et al. FT-IR (Bruker, Germany), Vario EL III Elementar elemental
2009; Li et al. 2008; Farinella et al. 2008; Anwar et al. 2010; analyzer (GmbH, Germany), and S-3400N II SEM (Hitachi,
Tan et al. 2010) have been reported for the removal of Pb. Japan). The adsorption mechanism was characterized by PHI
When using these waste materials as adsorbents, chemical or 5000 VersaProbe XPS (UlVAC-PHI, Japan).
physical modification is often required to increase adsorption
capacity and decrease some organic materials released into
solutions. Carbonization (Kazemipour et al. 2008; Depci et al. Standard solution and reagents
2012; Kongsuwan et al. 2009) and chemical modification with
acid (Lochananon et al. 2008), alkali (Sousa et al. 2010), and The stock standard solution for Pb (1,000 mg L−1) was pur-
different reagents (Mondal 2009; Li et al. 2010; Argun et al. chased from China National Measuring Science Research
2009) are common modification methods. Although the Institute (Beijing, China). Standard solutions were prepared
above-mentioned adsorbents have been studied for the remov- by appropriate dilution of the stock solutions daily. Analytical
al of Pb for many years, searching of new economical, easily grade reagents and double-distilled water (DDW) were uti-
available, and highly effective adsorbents is still an active lized unless otherwise specified.
research field.
Garlic peel, as a kind of easily available agricultural waste Preparation of native garlic peel and mercerized garlic peel
because of large consumption of garlic in daily life can be an
alternative adsorbent for more costly wastewater treatment Native garlic peel Native garlic peel used in this work was
processes. As we all know, garlic peel is rich in hydroxyl, collected from the local vegetable market in Nanjing, China.
carboxyl, sulfate, and amino groups, which can be bonded The peel was washed several times with tap water and DDW
with metals ions. The main objective of the present paper is to to remove surface impurities. Then it was boiled for 30 min,
compare native garlic peel and mercerized garlic peel as filtered out, and dried in an oven at 60 °C for 24 h. The dried
adsorbents for removing Pb from water solutions. The two material was ground and sieved to desired mesh size (100–
materials were first characterized by elements analysis (EA), 300 μm) and placed in a desiccator for further study.
Fourier transform infrared spectrometer (FT-IR), and scanning
electron microscope (SEM), and then some parameters Mercerized garlic peel Ten grams dried native garlic peel was
influenced on the adsorption rates such as pH, contact time, treated with 200 mL 5 mol/L NaOH and stirred for 4 h at
adsorbent doses, and the initial concentration on the removal 25 °C. Then, it was filtered and washed with DDW up to pH 7.
2056 Environ Sci Pollut Res (2014) 21:2054–2063

Mercerized garlic peel was dried in an oven at 105 °C for 1 h Table 1 The percentages of main elements in garlic peels by element
analysis
and left to cool in a desiccator.
Material C (%) N (%) O (%) H (%) S (%)

Adsorption experiments Native garlic peel 37.01 1.04 47.71 4.22 0.81
Mercerized garlic peel 36.01 1.47 48.79 4.11 1.02
All the adsorption studies were carried out in batch modes.
Briefly, 10 mL of sample solution containing the desired quan-
which contains large number of functional groups such as
tity of Pb was placed in a 20-mL conical glass test tube together
hydroxyl, amino, and carboxyl groups. The treatment of garlic
with a certain adsorbent. After that, the mixture was immersed
peel with aqueous sodium hydroxide can eliminate a large
into an ultrasonic bath performed at 40 kHz of ultrasound
amount of hemi-cellulose, lignin, and pectin (Borysiak 2012),
frequency and 100 W of power for a required time to accelerate
whose main components are carbohydrates. Hence, we can
the progress of adsorption and then centrifuged at 4,000 rpm for
conclude that mercerization treatment diminishes the percent-
10 min. After this progress, supernatant was collected utilizing a
age of C and H partially.
0.45-μm membrane filter, and the final Pb concentration in the
filtrate as well as in the initial solution was determined by FAAS.
The effect of initial pH on the recovery Pb(II) ions was FT-IR
evaluated at a pH range from 1 to 7. The adsorption studies
were also investigated in batch experiments as function of metal For the purpose of seeking functional groups capable of metal
ion concentration (1–200 mg/L), adsorbent dosage (1–100 mg), sorption, the garlic peels before and after mercerization were
and contact time (1–120 min) for maximum adsorption. The characterized with FT-IR from 4,000 to 400 cm−1, and the
removal percentage (R%) of Pb was calculated for each run by results were presented in Fig. 1. As observed in Fig. 1 A, B, a
following expression: strong band at 3,394.02 cm−1 was attributed to either –OH or –
NH group, and a band at 2,919 cm−1 was assigned to C–H
R% ¼ ðC o −C e Þ=C o  100 %
stretching variation. The peak around 1,642 cm−1 showed in
both spectra corresponded to C=C or C=N groups, 1,425 cm−1
where C o and C e are the initial and equilibrium concentration was related to C–H bending variation, and the peak at
of Pb (in milligrams per liter), respectively, in the solution. 896 cm−1 indicated the presence of C–C stretching variation
Adsorption capacity was calculated by: of carbohydrate ring. The most significant change observed in
Fig. 1 was the peak at 1,738 cm−1 corresponding to C=O
Q ¼ ðC o −C e ÞV =M stretching variation disappeared after the mercerization, and
the same phenomenon was also found in mercerized sisal
fibers (Kim et al. 2010). Moreover, the comparatively strong
where Q is the adsorption capacity (in milligrams per gram),
peaks at 1,052 cm−1 representing C–O bending variation or S–
C o is the initial concentration of metal in solution (in milli-
O stretching variation displayed in native garlic peel was
grams per liter), C e is the equilibrium concentration of metal
shifted to 1,062 cm−1 found in mercerized garlic peel. These
in solution (in milligrams per liter), V is the volume of metal
results indicated that the surface of garlic peel after the mer-
ion solution (in liters), and W is the weight of the adsorbent (in
cerization process was evidently changed, but the chemical
grams).
structure in the interior of the garlic peel was not significantly
affected.

Results and discussion

SEM
EA
In order to get direct information of surface characteristics and
For determination of major components of the native garlic morphology of native garlic peel and mercerized garlic peel,
peel and mercerized garlic peel, the elemental analysis was the SEM investigations were conducted and Fig. 2 depicted
carried out, and the results were shown in Table 1. It could be the SEM images of the two materials. It could be seen from
seen that after mercerization treatment of garlic peel, the Fig. 2a, b that the surface of native garlic peel was porous,
proportion of C and H were decreased, which agreed well rough, and irregular. After mercerization, the surface was
with the reference reported by (Júnior et al. 2009). As we all contrasted into disrupted and wrinkled obviously as observed
know, garlic peel is a kind of plant fiber and principally in Fig. 2c, and more pores became smaller as shown in Fig. 2d
consists of cellulose, hemi-cellulose, and pectin substances, because of the aggressive action of NaOH which increased the
Environ Sci Pollut Res (2014) 21:2054–2063 2057

Fig. 1 IR spectra of native garlic

140
peel (A), mercerized garlic peel
(B), native garlic peel loaded Pb

120
(C) and mercerized garlic peel
loaded Pb (D)
A

100
Transmittance (%)
80
B
C

60
40
D

20
0
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber cm

surface area for adsorption and thus leading to much higher Pb2+ on native garlic peel and mercerized garlic peel reached 7
adsorption capacity. and 9 mg/g, respectively, and then remained constant.
As could be seen from above, nearly the same trend of
adsorption behavior of Pb on native garlic peel and mercerized
Effect of pH garlic peel could be found during pH 1–7. This may be because
some functional groups were protonated and positive-charged
pH is one of the most important parameters affecting adsorp- at low pH. As pH increased, the adsorption surface became less
tion process because it governs the existing states of metals and positive, and therefore electrostatic attraction between Pb2+
also the dissociation of active functional groups possessing and garlic peel surface was likely to be increased, which
acid–base properties on the surface of adsorbent. The effect resulted in the increasing adsorption capacity of Pb2+. When
of pH on the removal of Pb2+ was evaluated in the range of 1– pH was reached 3, constant adsorption capacity was obtained,
7, and the results were illustrated in Fig. 3. As observed, the which may be due to the formation of complexes between Pb2+
adsorption capacity of Pb2+ on both native garlic peel and and functional groups of garlic peel. The most different ad-
mercerized garlic peel was improved with the increase of pH sorption behavior of Pb2+ on native garlic peel and mercerized
from 1 to 3. After pH was higher than 3, adsorption capacity of garlic peel lied in the adsorption capacity, which may be due to

Fig. 2 SEM images of native

garlic peel (a, b) and mercerized
garlic peel (c, d)
2058 Environ Sci Pollut Res (2014) 21:2054–2063

14 adsorption sites on both materials were available for adsorp-

Native garlic peel tion of the Pb2+. After the initial Pb2+ concentration was
12 Mercerized garlic peel higher than 50 mg/L, adsorption capacity of native garlic peel
was obtained about 51 mg/g and then remained constant.
10
However, adsorption capacity of mercerized garlic peel could
Q (mg g )

rise up to 109 mg/g at equilibrium when the initial Pb2+

-1

8
concentration was higher than 100 mg/L. Adsorption capacity
6 on both materials was kept unchanged at higher Pb2+ concen-
tration mainly due to relatively higher Pb2+ concentration
4
compared with availability of adsorption sites. Moreover, in
2 the comparison of native garlic peel, the remarkably enhanced
adsorption capacity of mercerized garlic peel was probably
0 because of a large number of active absorbed sites. And the
1 2 3 4 5 6 7
data achieved were further applied to explore the isotherm
pH
study of the adsorption process.
Fig. 3 Effects of pH on the adsorption capacity of Pb on native garlic
peel and mercerized garlic peel. C Pb 10 μg mL−1; contact time 15 min,
dosage of adsorbent 10 mg Effect of contact time

more active functional groups available for Pb on mercerized Adsorption is a time-dependent process, and equilibrium is
garlic peel. Hence, pH 5.0 was used in the remaining studies to attained only after exposing adsorbents to the sample solution
avoid lead precipitation, and the studies about adsorption for a “long” period of time. It is therefore important to evaluate
mechanism were carried out in the latter section. the effect of contact time on the adsorption capacity of Pb2+. A
series of contact time varying from 1 to 120 min were inves-
Effect of initial metal concentration tigated, and the results were shown in Fig. 5. The adsorption
capacity of Pb2+ ion on both materials increased with contact
The initial concentration of Pb2+ in sample solution plays a time, and the adsorption equilibrium was both achieved after
significant role as a driving force to overcome the mass 40 min for native garlic peel and mercerized garlic peel. It
transfer resistance between the solution and solid adsorbents. should be pointed out that the adsorption capacity of Pb2+ on
Adsorption experiments were conducted with varying initial the both materials was initially high which was probably due to
Pb2+ concentrations from 1 to 200 mg/L, and the results were the availability of large active sites on the surface of adsor-
shown in Fig. 4. As indicated, adsorption capacity improved bents. When the surface adsorption sites became exhausted,
rapidly with the increase of initial Pb2+ concentration ranging the adsorption capacity was controlled by the rate of transport
from 1 to 50 mg/L on native garlic peel and from 1 to 100 mg/ from the exterior to the interior sites of the adsorbent particles.
L on mercerized garlic peel, which was because sufficient In all subsequent experiments, contact time was maintained at
120
120

100
100

80 Native garlic peel

Mercerized garlic peel 80
Q (mg g )
-1

60
Q (mg g )
-1

60

40
40
native garlic peel
20 mercerized garlic peel
20

0 50 100 150 200 0

0 20 40 60 80 100 120
-1
Co (mg L ) Contact time (min)
Fig. 4 Effects of initial concentration on the adsorption capacity of Pb on Fig. 5 Effects of contact time on the adsorption capacity of Pb on native
native garlic peel and mercerized garlic peel. Contact time 30 min; pH 5; garlic peel and mercerized garlic peel. C Pb 150 μg mL−1; pH 5; dosage of
dosage of adsorbent 5 mg adsorbent 5 mg
Environ Sci Pollut Res (2014) 21:2054–2063 2059

40 min, which was considered sufficient for the removal of where q t (in grams per milligram) is the amount of adsorption
Pb2+. And the data obtained were further used to evaluate the at time t (in minutes), k 2 (grams per milligram minute) is the
kinetic parameters of the adsorption process. rate constant of the pseudo-second-order kinetic adsorption,
and q e is the equilibrium adsorption capacity. The values of
K 2 and q e could be obtained from the intercept and slope,
Effect of adsorbent dosage respectively, of the plot of the experimental t/q t versus t, and
the results were shown in Table 2. As could be seen, the q e
Adsorbent dosage is an important parameter because it deter- values were very close to the experimentally determined ones,
mines the capacity for a given adsorbent. The adsorption which suggested that the pseudo-second-order model fitted
studies of Pb2+ on both materials were employed by varying the adsorption kinetics of Pb2+ on both kind garlic peels very
the quantity of adsorbent from 1 to 100 mg, and the results well.
were displayed in Fig. 6. As expected, for 150 g/L Pb2+, the
removal efficiency of Pb2+ on both materials increased with Isotherms studies
increasing adsorbent dose and then kept constant. The notable
difference between native garlic peel and mercerized garlic Adsorption isotherms describe the interaction between adsor-
peel was the removal efficiency, and the former was always bent and adsorbate and are conductive to design adsorption
lower than the latter, which was due to the more reactive systems for a given metal ions. The Langmuir isotherm model
absorbed sites supplied by mercerized garlic peel. So, 80 mg was widely used to fit the experimental data derived from
native garlic peel and 60 mg mercerized garlic peel were native garlic peel and mercerized garlic peel. Langmuir iso-
accepted as operational dosage for the rest of the batch therm equation could be expressed in the following form:
experiments.
Ce 1 1
¼ þ
Kinetics studies qe k L Qmax Qmax C e

Study of sorption kinetics provides valuable insight into the

reaction pathways and in turn controls the residence time of where C e is the concentration in the solution at equilibrium, q e
adsorbate uptake at the solid–solution interface. The pseudo- (in milligrams per gram) is the equilibrium binding capacity,
second-order kinetic model has been extensively used to fit k L (in liters per milligram) is the Langmuir adsorption equi-
the experimental kinetic adsorption data, and the linearized librium constant related to the binding sites affinity, and Q max
pseudo-second-order kinetic equation is often used as the (in milligrams per gram) is the maximum binding capacity
following form: often used to quantify and contrast the performance of differ-
ent sorbents.
t 1 t Two linearized plots of C e/q e versus C e were fitted, and
¼ þ
qt k 2 qe 2 qe Q max and K L were calculated from the slopes and interceptions
of different lines, respectively, corresponding to different mate-
rials and listed in Table 3. As observed, high correlation coeffi-
100 cients of the two linearized Langmuir equations displayed a
good agreement between the parameters and confirmed the
80
monolayer adsorption of Pb2+ on both garlic peels. It should
be noted that the mercerized materials showed higher capacities
Removal percentage (%)

60
than native garlic peel, which agreed well with the report of
Gurgel et al. (2008). According to the report of Ass et al. (2006),
Native garlic peel
the mercerization treatment improved the material’s surface area
40 Mercerized garlic peel
and also made hydroxyl groups of the materials more accessible,
resulting in large enhanced adsorption capacity. In order to
20

Table 2 Pseudo-second-order parameters for the adsorption of Pb2+ on

0
garlic peels
0 20 40 60 80 100 Material q e (mg/g) k 2 (g/(mg min)) R2
Adsorbent dosage (mg)
Fig. 6 Effects of the dosage of absorbents on the adsorption capacity of Native garlic peel 58.04 0.01593 0.99
Pb on native garlic peel and mercerized garlic peel. C Pb 150 μg mL−1; Mercerized garlic peel 105.82 0.002619 0.99
pH 5; contact time 40 min
2060 Environ Sci Pollut Res (2014) 21:2054–2063

Table 3 Langmuir parameters for adsorption of Pb2+ on garlic peels binding energy of O and N was observed for native garlic peel
Material Q max (mg/g) K L (L/mg) R 2 displayed in Fig. 7d, f, and the possible reason for these was
due to the formation of Pb-O or Pb-N which would decrease
Native garlic peel 51.73 0.1303 0.99 the electronic density around O and N atoms (Sun et al. 2006).
Mercerized garlic peel 109.05 0.2320 0.99 These XPS results revealed that Pb was really reserved on both
garlic peels through bonding with O atom or N atom existed on
the surface of materials and chelation may be an important and
understand these results better, it is necessary to study the principal mechanism for the removal of Pb, which is in good
adsorption mechanism. agreement with FT-IR results.
Although the adsorption mechanism of native and mercer-
Adsorption mechanism ized garlic peel was primarily similar, the adsorption capacity
of mercerized garlic peel was higher than that of native garlic
In order to evaluate adsorption mechanism of Pb on native peel, which was mainly due to mercerization process. The
garlic peel and mercerized garlic peel, the characterization for treatment of mercerization can remove cementing substances
attraction of the absorbent to Pb was performed by FT-IR such as hemi-cellulose, lignin, and pectin on the surface of
conducted at pH 5, and the results were described in Fig. 1 fiber (Borysiak 2012); improve the surface area; and facilitate
C, D. The FT-IR spectra of native garlic peel and native garlic other reagents penetrate into the cavities of fiber easily,
peel absorbed with lead ions depicted in Fig. 1 A, C revealed resulting in a rearrangement of the crystal packing of chains
that the peak of C=O groups shifted significantly from 1,738 from native cellulose I with chains aligned in parallel to cellu-
to 1,696 cm−1, C=C groups shifted from 1,425 to 1,403 cm−1, lose II with antiparallel chains (Beatriz et al. 2006; Zugenmaier
and C–C or S–O groups shifted from 1,052 to 1,018 cm−1. 2001). Furthermore, the conversation of cellulose from I to II
Similar transitions of these oxygenic groups were observed for in garlic peel after mercerization treatment can decrease in the
mercerized garlic peel and mercerized garlic peel loaded with degree of polymerization and crystalline of the fiber and in-
Pb2+. However, the difference in the peak of C=O groups, crease amorphous cellulose (Nishimura and Sarko 1987),
C=C groups, and C–C or S–O groups were shifted from 1,642 which makes the hydroxyl groups of cellulose macromolecules
to 1,641, 1,425 to 1,402, and 1,062 to 1,051 cm-1, respective- more accessible (Pusic et al. 1999) and thus leads to higher
ly. According to the above results, it could be speculated that adsorption capacity of mercerized garlic peel.
Pb2+ may be chelated with O atom existed in both garlic peels,
which thus led to the transformations in wave number of
oxygenic groups. Conclusions
In order to validate the explanation mentioned above about
adsorption mechanism of Pb2+ on both garlic peels, the char- Native garlic peel and mercerized garlic peel have been suc-
acterization was conducted by XPS also. XPS is a kind of cessfully used and critically compared as adsorbents to re-
powerful method for the determination of the chemical state of move Pb2+ from aqueous solution. Based on the study, it can
a solid surface, i.e., the oxidation number and the electronic be concluded that garlic peel after mercerization can be more
interactions with neighboring elements from the first coordi- effective with higher capacity under optimized pH, contact
nation shell by binding energy of electrons in molecules. For time, and adsorbent dosage. The equilibrium sorption data for
the sake of evaluating the adsorption progress of Pb2+ on garlic both garlic peels fitted well with Langmuir adsorption iso-
peel further, XPS was employed in this work and the spectra of therm, and the adsorbent–adsorbate kinetics exhibited pseudo-
garlic peel and Pb-loaded garlic peel were shown in Fig. 7. As second-order model. The both garlic peels were characterized
displayed in Fig. 7a, c, the principal elements were C, O, N, by EA, FT-IR, and SEM, and the results indicated the presence
and S in the XPS spectra of both native garlic peel and of C, H, O, N, and S elements and the main functional groups
mercerized garlic peel; significant bands with binding energies of C=O, C–O, and S–O. As contrasted to native garlic peel,
of 137.6 eV were newly appeared after the two garlic peels mercerized garlic peel has lower polymerization and crystal-
were treated with Pb, which was the characteristic of lead line and more accessible functional hydroxyl groups, which
oxalate compounds rather than lead hydrate according to the resulted in higher adsorption capacity. The FT-IR and XPS
Handbook of X-Ray Photoelectron Spectroscopy edited by PE analyses of both garlic peels before and after loaded with Pb2+
Corp. (Moulder et al. 1992). In Fig. 7b, a peak appeared at showed that lead was adsorbed on the garlic peels through
530.6 eV corresponded to O atoms in mercerized garlic peel, surface complex with O atom. These above results revealed
and the bind energy was shifted to 531.2 eV after loaded with that as compared with native garlic peel, mercerized garlic
Pb2+. The binding energy of 398.6 eV shown in Fig. 7e was peel can be a more attractive alternative adsorbent material at
responded to N atoms in mercerized garlic peel and was shifted the commercial point of view because of faster sorption up-
to 398.8 eVafter absorbed with Pb2+. Similar transformation of take and higher capacity.
Environ Sci Pollut Res (2014) 21:2054–2063 2061

a c
16000
16000 Mercerized garlic peel Native garlic peel
14000 C1s
Mercerized garlic peel-Pb
Native garlic peel-Pb
14000
C O 12000 O1s
1s 1s
12000
10000
10000
8000

CPS
N1s
CPS

8000 N
1s 6000
6000
4000
Pb4f
Pb
4000 4f S2p
2000
S2p
2000
0
0
-2000
0 200 400 600 800 1000 0 200 400 600 800 1000
Binding energy / ev Binding energy / ev

b d
4000
O in mercerized garlic peel-Pb 3000 O in native garlic peel
O in mercerized garlic peel O in native garlic peel - Pb
3500 531.1
531.2
3000 2500

2500
2000
CPS
CPS

2000
530.8
1500
1500

1000 530.6 1000

500
500
0
520 525 530 535 540 545 520 525 530 535 540 545
Binding energy / eV Binding energy/ eV

e f
600 900

N in mercerized garlic peel N in native garlic peel

N in mercerized garlic peel-Pb 800
N in native garlic peel-Pb
550
398.6 398.8
399.6
398.6
500 700
CPS
CPS

450 600

400 500

350 400

390 395 400 405 410 415 390 395 400 405 410 415
Binding energy / ev Binding energy / ev

Fig. 7 XPS spectra of mercerized garlic peel before and after extraction (a), native garlic peel before and after extraction (c), O1s and O1s-Pb in mercerized
garlic peel (b) and O1s and O1s-Pb in native garlic peel (d), N1s and N1s-Pb in mercerized garlic peel (e), and N1s and N1s-Pb in native garlic peel (f)

Acknowledgments This work was supported by Fundamental Re- National Natural Science Fund of China (21275069, 21121091), National
search Funds for the Central Universities (KYZ201220), Basic Research Jiangsu Postdoctoral Research Funds (1001002C), and Analysis & Test
Program of China (973 program, 2009CB421601, 2011CB911003), Fund of Nanjing University.
2062 Environ Sci Pollut Res (2014) 21:2054–2063

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