Chemosphere xxx (2013) xxx–xxx

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Sustainable sorption strategies for removing Cr3+ from tannery process

wastewater
Antonio De Martino ⇑, Marianna Iorio, Renato Capasso
Dipartimento di Agraria, Università di Napoli ‘‘Federico II’’, Via Università 100, 80055 Portici, Italy

h i g h l i g h t s

3+
 The removal of Cr by simulated and tannery wastewaters is studied.
3+
 Use of a LDH-organic matter complex is adopted to sorb Cr .
3+
 The removal of Cr by tannery wastewaters is lower than by simulated wastewaters.
 LDH–Mg–Cr is prepared by using of tannery wastewaters.
3+
 Preparation of LDH–Mg–Cr allowed an almost total removal of Cr .

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

Article history: Two different strategies for the removal of trivalent chromium (Cr3+) from contaminated water are
Received 27 December 2012 reported. The first one is based on the sorption process on an organo-mineral complex, named LDH–
Received in revised form 9 March 2013 HP, obtained in turn by sorption of polymerin, the humic acid-like fraction occurring in olive oil mill
Accepted 29 March 2013
wastewater, on a layered double hydroxide (LDH) of magnesium and aluminium with carbonate in the
Available online xxxx
interlayer. This sorption process is preliminary developed on simulated wastewater (SW) as theoretical
model and successively applied on tannery process wastewaters (TPWs) natively containing Cr3+. The
Keywords:
removal of Cr3+ from TPW is lower than that observed for SW, because of the large compositional vari-
Layered double hydroxides
Polymerin
ability of TPW. The second one is based on the direct production of a LDH of magnesium and chromium
Chromium (Cr3+), using as starting material TPW, naming LDH–TPW the complex produced. This process allows the
Isotherm complete removal of Cr3+ from TPW and also the abatement of chemical oxygen demand, indicating to be
Kinetic a very promising purification process for an industrial application.
Tannery wastewater Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Many human activities as well as industrial or agricultural pro-
cesses are responsible for the increasing pollution of soils, sedi-
ments and waters from heavy metals. In the environment,
chromium predominantly exits in two oxidation states, the triva-
lent form Cr3+, and hexavalent form, Cr6+. Cr3+ naturally occurs in
the environment and small amounts are necessary in human and
animal diet, but an excess is extremely toxic because of the forma-
tion of relatively strong complexes with oxygen and donor ligands.
Moreover, Cr3+ is insoluble and thus immobile under ambient con-
ditions. Chromium is generally produced by chemical, tannery, tex-
tile and metallurgic industries. TPW are considered to be one of the
most polluting industrial activities in the world. Tanning processes
are classified according to the type of tanning reagent (tannins or
⇑ Corresponding author. Address: Dipartimento di Agraria, Università di Napoli
‘‘Federico II’’, Via Università 100, 80055 Portici, Italy. Tel.: +39 081 2539161; fax:
+39 081 2539202.
E-mail address: ademarti@unina.it (A. De Martino).
chrome) used to bind the collagen fibers. TPW contains blood,
dung, coat, proteins in solution and in suspension, animal fats, hair
and other. Moreover, calcium, sulfide, sulfate, chloride, organic and
inorganic acids, tannins, and trivalent chromium are usually pres-
ent in very high concentrations. Many different methods, as sorp-
tion, coagulation, ion exchange, filtration, precipitation and
membrane process, are available to treat TPW.
The sorption method, for the low maintenance costs, high effi-
ciency and ease of operation is one of the most relevant that has
been successfully applied to remove heavy metals and organic
chemicals from hazardous wastes.
Layered double hydroxides (LDHs) are a class of lamellar com-
pounds also known as hydrotalcite-like clays for the structural
similarities to hydrotalcite, a mineral with the formula Mg6Al2(-
OH)16CO34H2O. The hydrotalcite structure results from the stack-
ing of brucite-like layers [Mg(OH)2] containing a positive residual
charge arising from the partial isomorphous substitution of Mg2+
with Al3+. The anions present in the interlamellar spaces balance
the positive excess charge.

0045-6535/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2013.03.051

Please cite this article in press as: De Martino, A., et al. Sustainable sorption strategies for removing Cr3+ from tannery process wastewater. Chemosphere
(2013), http://dx.doi.org/10.1016/j.chemosphere.2013.03.051
2 A. De Martino et al. / Chemosphere xxx (2013) xxx–xxx
Actually there is an increasing interest for LDHs because of their
interesting physico-chemical properties. In fact, the large surface
area, high anion exchange capacity and good thermal stability
make them very interesting sorbents to remove surfactants (Pavlo-
vic et al., 1997), phenols (Barriga et al., 2002), pesticides (Pavlovic
et al., 2005) and inorganic oxyanions (Goh et al., 2008) from pol-
luted waters. The synthesis of LDHs occurs prevalently by direct
and indirect methods as co-precipitation (Ulibarri and Hermosin,
2001) or anionic exchange (Leroux et al., 2001). Advanced applica-
tions have led to synthesize a large range of LDHs varying the diva-
lent or trivalent cation and the inter-lamellar counter-ion. With the
aim to remove cationic heavy metals from contaminated waters,
LDHs have been also intercalated with anionic ligands (Perez
et al., 2006; Pavlovic et al., 2008; Anirudhan and Suchithra, 2008).
In previous studies we demonstrated that polymerin, the hu-
mic-acid-like fraction recovered from olive oil mill waste waters
(OMWWs) (Capasso et al., 2002) is able to remove cationic heavy
metals and pesticides from wastewater (Capasso et al., 2004; Sann-
ino et al., 2008). More recently, we demonstrated that two LDH-
polymerin complexes (LDH–CO3–HP and LDH–CO3–LP) are able
to sorb both arsenate or zinc from simulated wastewater and that
these complexes are more stable than the free LDH–CO3 (Iorio
et al., 2010).
The significant sorption capacity by LDH–CO3–HP of heavy me-
tal cation (Iorio et al., 2010) strongly suggests to develop a study
also on the sorbing capacity by this kind of LDH of Cr3+ occurring
in TPW.
For this reason a study is performed on: (i) the sorption capacity
of LDH–CO3–HP (here LDH–HP) to remove Cr3+ from SW as theo-
retical sorption model, than (ii) the application of this model in
laboratory for the removal of Cr3+ from TPW. A further investiga-
tion is performed to remove Cr3+ present in TPW by direct produc-
tion of a LDH–Mg–Cr, utilizing the same Cr3+ occurring in TPW.
This is the first paper describing the production of a LDH con-
taining Cr3+, using as basic material a wastewater like TPW, with
the objective of a possible industrial application finalized to a puri-
fication of TPW.
2. Materials and methods
2.1. Preparation of the sorbents
Polymerin is prepared as reported by Iorio et al. (2010). Mg–Al
layered double hydroxide with carbonate in interlayer (LDH) is
prepared by direct co-precipitation at room temperature according
to Ulibarri et al. (2001). The final pH of LDH preparation was 13. An
organo-mineral complex is prepared by adding one gram of polym-
erin to a suspension containing 4.0 g of LDH in 1.6 L of deionized
water, under vigorous stirring (without pH variation). After 72 h,
the precipitate is washed, than dialyzed, and finally freeze-dried.
The matrix so obtained is called LDH–HP (where HP means high
content of polymerin).
2.2. Chemical and physico-chemical analysis
3+
Cr is determined by AAS using a Perkin–Elmer model 3030 B
atomic absorption spectrometer equipped with deuterium-arc
background correction. An air–acetylene flame was used as the
atomization source. Stock standard solutions of Cr3+ are obtained
from BDH Reagents (Poole, UK). The average and standard devia-
tion of three absorption measurements were recorded for each
sample. Spectrophotometric analysis are carried out by a UV–visi-
ble Perkin–Elmer spectrophotometer. Diffuse Reflectance Infrared
Fourier Transform (DRIFT) spectroscopy analysis are performed
using a Perkin–Elmer Spectrum One FT-IR. X-ray diffraction
(XRD) analysis is carried out on a Rigaku Geigerflex D/Max IIIC
Please cite this article in press as: De Martino, A., et al. Sustainable sorption strategies for removing Cr3+ from tannery process wastewater. Chemosphere
(2013), http://dx.doi.org/10.1016/j.chemosphere.2013.03.051
diffractometer. Elemental analysis is performed using a Fisons EA
1108 elemental analyzer for hydrogen, carbon, nitrogen, and
sulfur. Chloride and sulfate are analyzed by ionic chromatography
using a Dionex DX-300 Ionic Chromatograph (Dionex Co., Sunny-
vale, CA), an Ion-Pac AS4A column and as eluent a mixture of
1.8 mM of Na2CO3 and 1.7 mM of NaHCO3 at a flow rate of
2.0 mL min1, and a CD20 Conductivity Detector combined with
auto-suppression.
2.3. Sorption methodology
Sorption uptake in SW is carried out by a batch equilibration
technique at 25 ± 1 °C, pH 5.0 and a solid/liquid ratio of 2.5. Exper-
iments are performed by diluting of 25 mM Cr(NO3)39H2O stock
solution. Matrices before sorption are dried at 100 °C for 1 h. After
incubation, the samples are centrifuged at 7000 rpm for 10 min
and the supernatants analyzed by atomic absorption spectrometry
(AAS). Experiments are conducted in duplicate. Metal solution
without sorbent (blank samples) were also analyzed under the
same experimental conditions, with the aim to identify potential
losses of Cr3+ by processes of precipitation or other. The amount
of Cr3+ that precipitated at pH 5.0 is <2% (Da Fonseca et al., 2006).
2.4. Theoretical studies
2.4.1. Effect of time
Aliquots of 500 mg of LDH–HP are suspended in 200 mL of
5.77 mM of Cr(NO3)39H2O in glass bottles with screw caps. At se-
lected times, the bottles are hand-shaken, the contents are allowed
to settle for 10 min and 1 mL of supernatant solution is sampled
and analyzed by AAS. The periodical removal of such a small
amount of supernatant is assumed to have no influence on the
sorption.
2.4.2. Sorption isotherms
Sorption isotherms are performed ranging the concentration of
Cr3+ from 9.6  102 to 5.77 mM. Experiments are carried out by
adding 40 mg of LDH–HP to a final volume of 16 mL. After 24 h
the samples are centrifuged and supernatants analyzed by AAS.
2.5. Data analysis
For the kinetic data the amount of Cr3+ sorbed (qt) at time t is
calculated using the mass balance:
VðC i  C e Þ
qt ¼ ð1Þ
m
where V is the solution volume (L), m is the amount of sorbent (g)
and Ci and Ct (mM) are the initial and at time t Cr3+ concentrations.
Kinetic data are processed using the pseudo-first order model
(Namasivayama and Yamuna, 1995) and pseudo-second order
model (Ho and McKay, 1999).
The first equation can be written as:
lnðqe  qt Þ ¼ ln qe  k1 t ð2Þ
1
where k1 (min ) is the pseudo-first order rate constant, evaluated
from the slope of the plot of ln(qeqt) versus t; qt and qe (mmol g1)
are the sorption capacities at time t and equilibrium and t is the
time (min).
The second equation can be written as:
t 1 t
¼ þ ð3Þ
qt k2 q2e qe
where qe, qt and t are described above; k2 is the pseudo-second or-
der rate constant (g mmol1 min1); qe and k2 are calculated by
plotting t/qt versus t.
 A. De Martino et al. / Chemosphere xxx (2013) xxx–xxx
In order to distinguish the film diffusion and intraparticle diffu-
sion process the Weber–Morris’s equation (Weber and Morris,
1963) is used in the following form:
qt ¼ kp t 0:5 þ C
where C is the intercept and kp (mmol g1 min1) is the diffusion
rate constant which can be evaluated by the slope of the linear plot
of qt versus t0.5. The intercept of the plot reflects the boundary layer
effect.
For the sorption isotherms the amount of Cr3+ sorbed (q) is cal-
culated using the mass balance:
VðC i  C e Þ
q¼
m
where V is the solution volume (L), m is the amount of sorbent (g)
and Ci and Ce (mM) are the initial and equilibrium Cr3+
concentrations.
Langmuir equation is employed to fit Cr3+ equilibrium data:
Sm kC e
S¼
ð1 þ kC e Þ
where S is the amount of Cr3+ sorbed (mmol g1); k (L mmol1) is
the Langmuir constant related to the binding energy; Sm is the max-
imum amount of Cr3+ sorbed (mmol g1) and Ce is the equilibrium
concentration of Cr3+ (mM).
The sorption data are also analyzed according to the Freundlich
equation that can be written as follows:
1
S ¼ kF C eN
where S and Ce are defined in the equation reported above; kF
[(mmol g1)/(mmol L1)1/N] and N (dimensionless) are constants that
give estimates of the sorptive capacity and intensity, respectively.
The dimensionless constant separation factor RL is calculated as:
1 that polymerin is linked exclusively on the surface of the mineral
RL ¼
1 þ kC o
where Co is the highest initial concentration of adsorbate (mM), and
k (L mmol1) is Langmuir constant.
Experimental uncertainties are evaluated in vials without sam-
ples, which show that total uncertainty is less than 5% of the initial
concentrations. All of the experiments are performed in duplicate.
2.6. Removal of Cr3+ from TPW by sorption on LDH–HP
TPW is supplied by a plant localized in Casoria (Italy). Chemical
analysis of influent and successively of effluent trough LDH–HP are
carried out as described in Section 2.2 and in accordance with the
Standard Methods (APHA et al., 1998). Sorption experiments are
performed at pH 5.0 by mixing of 100 mL of TPW with 4.85 g of
LDH–HP.
2.7. Removal of Cr3+ from TPW by producing LDH–Mg–Cr (LDH–TPW)
LDHs are a class of sorbents very heterogeneous because during
their preparation is possible to vary both the divalent or trivalent
cation or the corresponding counter-ion in the interlayer. Conse-
quently, we intend to remove Cr3+ natively occurring in TPW by di-
rect production of LDH–TPW. Therefore, to 100 mL of TPW with a
Cr3+ content of 60 mM are added 100 mL of a solution containing
120 mM of Mg2+[(Mg(NO3)26H2O] in way to have a molar ratio
Mg:Cr of 2. This prepared was added to 100 mL of a solution con-
taining threefold excess of Na2CO3. The LDH–TPW was obtained at
a fixed pH of 5.0 by controlled addition of 0.1 M KOH solution (Del-
gado et al., 2004). After complete addition, the resulting slurry is
treated as previously described for LDH. To verify the formation
Please cite this article in press as: De Martino, A., et al. Sustainable sorption strategies for removing Cr3+ from tannery process wastewater. Chemosphere
(2013), http://dx.doi.org/10.1016/j.chemosphere.2013.03.051
3
of LDH–TPW the same procedure is repeated by substituting
TPW simply with a solution of Cr3+ salt [(Cr(NO3)39H2O], obtaining
the complex named LDH–CS (Delgado et al., 2004).
ð4Þ
3. Results and discussion
3.1. Characterization of the matrices
Some important chemical and physico-chemical properties of
polymerin, LDH and LDH–HP have been previously described by
Iorio et al. (2010) and reported for comparison in Table 1 of SI.
The distribution of polymerin relative molecular size determined
ð5Þ by calibrated molecular weight gel filtration chromatography indi-
cated that polymerin is composed of two subunits: the first with a
relative molecular weight of approximately 45 000 Da is composed
only of a free polysaccharide while the second with a relative
molecular weight between 3500 and 10 000 Da is composed of pro-
teins, melanins, and polysaccharides aggregated in a supramolecu-
lar status by a combination of covalent and hydrogen bonds and
ð6Þ CH/p interactions (Capasso et al., 2002). The E4/E6 ratio analysis
of the polymerin, which remained in the supernatant after sorption
onto LDH revealed that the small molecules present in the polym-
erin were more easily sorbed than the larger ones. The percentage
of polymerin in LDH–HP is 18.9% and, as expected, the content of
polysaccharaide, melanine and protein is much more low in the
complex with respect to polymerin (Iorio et al., 2010). The value
of PZC of LDH–HP is much more high than that of polymerin, but
very similar to that of LDH, indicating that the sorption of polym-
ð7Þ erin does not change significantly this property in LDH. The same
behavior is observed for the surface area. XRD analysis of
LDH–HP shows the characteristic pattern of crystalline lamellar
hydrotalcite-like material with sharp and symmetrical peaks. Basal
spacing, calculated from the d003 reflection, is very similar to LDH
(7.59 Å against 7.60 Å) (Fig. 1 of SI). This analysis demonstrates
ð8Þ
matrix, due to its high molecular weight. The DRIFT spectra of
LDH–HP shows the characteristic signals of hydrotalcite (see LDH
for comparison) and small and broad signals attributable to the
polymerin at 1541 cm1 and 1060 cm1 attributable to C@C of
the aromatic rings of melanin and ACAOH sugar groups, respec-
tively (Fig. 2 of SI). As reported by Iorio et al. (2010), LDH–HP at
pH 4.0 appears to be more stable than LDH. In fact, LDH–HP shows
a lower dissolution and a percentage of recovery more high than
that observed for LDH. The higher stability of the complex was
attributable very likely to the polymerin macromolecules that cov-
er and protect the surface of the mineral.
3.2. Removal of Cr3+ by sorption on LDH–HP
An important factor of the sorption process is the pH of
medium. The sorption of Cr3+ by sorbent in aqueous system is cor-
related with pH of solution which, in turn, depends on the surface
charge of the matrix utilized. In solution, without pH adjustment,
LDH–HP presents a basic pH (pH > 9.0) and consequently Cr3+ is
removed via precipitation process. In fact, the principal species of
chromium corresponding to the equilibrium constant are as
following (Wu et al., 2008):
Cr3þ þ H2 O $ CrðOHÞ2þ þ Hþ pK ¼ 4:0
CrðOHÞ2þ þ H2 O $ CrðOHÞþ2 þ Hþ pK ¼ 5:7
CrðOHÞþ2 þ H2 O $ CrðOHÞ3 þ Hþ pK ¼ 8:3
The solubility limit can be calculated using the following reac-
tion and the Ksp value:
4 A. De Martino et al. / Chemosphere xxx (2013) xxx–xxx
0,7
0,6
Cr+3 sorbed (mmol g-1)
0,5
0,4
0,3
0,2
0,1
0,0
0 200 400 600 800 1000 1200 1400
Time (min)
Fig. 1. Effect of time on the sorption of Cr3+ on LDH–HP at pH 5.0.
CrðOHÞ3 $ Cr3þ þ 3OH Ksp ¼ 1  1030
30
By taking the Ksp value of Cr(OH)3 as 1  10 and an initial Cr
concentration of 5.77 mM, the pH value at which the precipitation
start is 4.75. Considering that polymerin has a pKa of 4.5 (Capasso
et al., 2002), the decreasing of pH under this value implies that
the functional groups of the organic component become prevalently
protonated causing a strong repulsion with Cr3+ in solution. There-
fore, kinetics and isotherms were performed at constant pH of 5.0.
Fig. 1 shows the amount of Cr3+ sorbed in dependence on time
at pH 5.0. The amount sorbed is expressed as difference between
the initial Cr3+ concentration (mmol g1) and the amount of Cr3+
sorbed (mmol g1) at any time t. Sorption is produced in two
phases: a very fast one occurring in 120 min and a second one
more slow that is completed in 480 min. The time profile of metal
uptake is a single, smooth and continuous curve leading to satura-
tion, suggesting the possible monolayer coverage of metal ion onto
the surface of the sorbents. Because the activity of the LDH based
sorbents is governed by the pH, at pH 5.0 the predominant specie
of chromium in solution is Cr(OH)2+ (Da Fonseca et al., 2006; Wu
et al., 2008) and consequently the sorption occurs rapidly by ionic
exchange and complexation of Cr3+ with the functional groups of
polymerin. Capasso et al. (2004) report that sorption mechanism
of Cr3+ on polymerin occurrs by ion exchange of the native Ca2+,
K+, and Mg2+ with Cr3+ and a concomitant complexation with the
AOH groups of the polysaccharide component of this biosorbent.
Moreover, a second mechanism due to precipitation phenomena
of Cr3+ induced by the higher surface pH of LDH is not to be
excluded.
Two kinetic models have been tested in the present study, in or-
der to explain the sorption process of Cr3+: (a) a pseudo-first-order
kinetic model and (b) a pseudo-second order kinetic model. In gen-
eral, in a first order reaction, independently on the initial concen-
tration of sorbate, the time for its half-life is constant. In a
second order reaction the time necessary for the half-life of sorbate
is inversely proportional to its concentration. The best-fit model
was selected on the linear regression correlation coefficient, r2, va-
lue. The parameters k1 and k2 of pseudo-first order and pseudo-
second order equations with the corresponding correlation coeffi-
cients (r2) are listed in Table 1. The results show that the pseu-
do-second-order model is the best model for description of the
kinetic data because the value of r2 is more close to 1 than that
of pseudo-first-order model. Moreover, the values of qe of the pseu-
do-second order are more close to the experimental sorption
capacity, qe, than that of the pseudo-first-order.
Please cite this article in press as: De Martino, A., et al. Sustainable sorption strategies for removing Cr3+ from tannery process wastewater. Chemosphere
(2013), http://dx.doi.org/10.1016/j.chemosphere.2013.03.051
Table 1
Pseudo-first and pseudo-second-order parameters for the sorption of Cr3+ onto LDH–
HP.
Pseudo-first-order Pseudo-second-order
q ea r2 r2
qe k1 qe k2
LDH–HP 0.56 0.46 0.006 0.96 0.61 0.06 0.99
a
Equilibrium sorption capacity obtained as experimental.
0,7
0,6
Cr+3 sorbed (mmol g-1)
0,5
1600
0,4
0,3
0,2
0,1
3+
0,0
0 10 20 30 40
Time (min0.5)
Fig. 2. The plot of intraparticle diffusion modeling of Cr3+ onto LDH–HP.
In order to clarify the mechanism and rate controlling steps
affecting the sorption kinetics, the kinetic experimental results
are fitted to the Weber’s intraparticle diffusion. If the regression
of qt versus t0.5 is linear and passes through the origin, then
intraparticle diffusion is the sole rate-limiting step. Generally,
three steps are involved during the sorption process (Lv et al.,
2006): (i) mass transfer of sorbate from the aqueous phase onto
the solid surface, (ii) sorption of solute on the surface sites and
(iii) internal diffusion of solute via either a pore diffusion model
or homogeneous solid phase diffusion model. During the present
investigation, step two has been assumed rapid enough with
respect to the other steps. As seen in Fig. 2, the plot present two
phases due to the different extent of sorption in the initial and final
phases of the experiment. In fact, in the initial stage, sorption is
due to boundary layer diffusion effect whereas, in the later stage
(linear portion of the curve) is due to the intraparticle diffusion
effect. However, the plot indicated that the intraparticle diffusion
was not the only rate controlling step because it does not pass
through the origin.
The sorption isotherms of Cr3+ are shown in Fig. 3 while the
corresponding Langmuir and Freundlich parameters in Table 2.
Based on correlation coefficient (r2) values (>0.98) it is observed
that the adsorption process can be best described by the Langmuir
model. The fact that this model fits the experimental data very well
may be due to homogenous distribution of active sites on sorbent
surface; since the Langmuir model assumes that the surface is
homogenous. The sorption isotherms are of Langmuir H-type (Giles
et al., 1974), indicating a high affinity behavior; in fact the sorption
is characterized by a rapid rise at a low Cr3+ equilibrium concentra-
tion. A sorption of 93% with an initial concentration of Cr3+ corre-
sponding to 0.384 mM is observed. The values of Sm by Langmuir
model corresponding to 0.64 mmol g1 can be compared with
other sorbents of literature as reported by Wu et al. (2008). The va-
lue of RL indicates an unfavorable (RL > 1), linear (RL = 1), favorable
(0 < RL < 1), or irreversible (RL = 0) sorption. The value of RL in the
present study is 0.040 indicating that the sorption is favorable.
 A. De Martino et al. / Chemosphere xxx (2013) xxx–xxx 5

0,8 Table 3
Main characteristics of tannery process wastewater.

Influent Effluent after sorption onto LDH–HPa

3+ 1
0,6 Cr (mmol L ) 32.1 8.1 (74.7%)
Cr+3 sorbed (mmol g-1)

pH 3.62 –
COD (mg L1) 3740 2340 (37.4%)
BOD5 (mg L1) 1520 1020 (32.9%)
Total solid (mg L1) 65 200 53 700
0,4
Chloride (Cl; mmol L1) 269.2 224 (16.8%)
Sulfate (SO2 1 218.6 157 (28.1%)
4 ; mmol L )

a
Sorption experiments were carried out at pH 5.0 with 100 mL of tannery
0,2 Experimental wastewaters and 4.85 g of LDH–HP.
Langmuir
Freundlich
1000 mL with an initial Cr3+ concentration of 32.1 mM is 0.77,
0,0
0 1 2 3 4 5
4.85, 24.2 and 48.5 g, respectively.
In order to test this model, TPW is used in laboratory studies to
Equilibrium concentration of Cr+3 (mM)
simulate a real situation. The main characteristics of the effluent
Fig. 3. Sorption isotherms of Cr3+ on LDH-HP at pH 5.0. are shown in Table 3. TPW is characterized by an acidic pH
(3.62) while the COD and BOD5 values are 3740 and 1520 mg
L1. Moreover, the influent is characterized by high concentration
of inorganic anions as chloride and sulfate (269.2 and 218.6 mM).
Table 2 The results show very significant differences between the theoret-
Sorption parameters of Langmuir and Freundlich isotherms. ical and real model and also comparing the compound concentra-
Langmuir isotherm parameters Freundlich isotherm parameters tions of influent versus the effluent. In particular, we observe a
Sm (mmol g1) k r2 RL kF (mmol g1) 1/N r2 lower sorption of Cr3+ (Table 3), more precisely 74.7%. As reported
LDH–HP 0.64 4.12 0.98 0.040 0.44 0.29 0.96 in Table 3 TPW has a large variability that could influence the re-
moval of Cr3+ from solution. In fact, the presence of undefined or-
The XRD patterns of the complex sorbent-Cr3+ (LDH–HP–Cr3+) ganic compounds probably generates competition phenomena for
(Fig. 1 of SI) show to be similar to those of the native precursor, the sorption sites on both the matrices. As a confirmation of this
but with a decreasing peak intensity. On the other hand no peaks hypothesis, we observe a reduction of COD and BOD5 (Table 3).
attributable to precipitation processes are observed. DRIFT spectra The chemical analysis of TPW after sorption evidences also a
of LDH–HP–Cr3+ (Fig. 2 of SI) indicate that Cr3+ is able to interact reduction of Cl and SO2 4 . This finding can be explained consider-

with both the sorbent components. In fact, as consequence of the ing that at pH of 5.0 the CO2 3 anions linked to the LDH are
sorption of Cr3+ the functional groups of polymerin C@O converted in CO2 by the following reaction:
(1723 cm1), C@C (1498 cm1), COO (symmetric signal at CO2 þ
$ HCO3 þ Hþ $ H2 CO3 $ H2 O þ CO2
3 þ 2H
1636 cm1 and asymmetric overlap on that at 1384 cm1) and
AOH of sugar (1070 cm1) present a greater vibrational freedom and successively replaced by Cl and SO2 4 anions present in
and appear more evident that in the native precursor. In addition, solution.
the disappearance of peaks at the value under 1000 cm1 indicate a Clearly the removal efficiency is correlated with the amount of
probably complexation of Cr3+ with the AOH of mineral sorbent utilized and only with low values of the chemicals in solu-
component. tion is possible to obtain the maximum efficiency of the process;
Summing the data of XRD and DRIFT analyses, we can conclude viceversa, the high concentration of the species in solution requires
that sorption of Cr3+ occurs by formation of complexes with the a further increase of the sorbent.
AOH groups of organic and inorganic component of the sorbent
and by ionic exchange with the functional group of polymerin. 3.4. Removal of Cr3+ from TPW by production of LDH–TPW

3.3. Removal of Cr3+ from TPW by sorption on LDH–HP
A hypothetical single-stage batch-sorption system is schemati-
cally represented in Fig. 3 of SI (Vadivelan and Vasanth Kumar,
2005). At t = 0 a solution of volume V (L) with an initial concentra-
tion Ci (mM) of Cr3+ is reduced to Ce (mM). The amount of sorbent
is m (g) and the Cr3+ concentration increases from q0 (mmol g1) to
q (mmol g1). Because at time t = 0, q0 = 0, the mass balance equa-
tion can be written as:
VðC i  C e Þ ¼ mðq  q0 Þ ¼ mq
Because the best fit for sorption of Cr3+ is obtained using the
Langmuir model, the Eq. (9) can be rearranged as:
m Ci  Ce
¼ Sm kC e
V 1þkC
e
Developing the Eq. (10), the theoretical amount of LDH–HP neces-
sary to reduce of 90% an effluent volume of 16, 100, 500 and
LDHs being sorbents very simple to prepare, cheap and very
efficient, they suggest to be used to reduce the Cr3+ content and
the organic and inorganic load of TPW, by preparing specifically
LDH–TPW. In order to have a comparison system, we firstly have
prepared a LDH of magnesium and chromium (LDH–CS) utilizing
two commercial salts of Cr3+ and Mg2+. The chemical formula of
LDH–CS is [Mg0.64Cr0.36(OH)2](CO3)0.18]0.4H2O with a molar ratio
Mg:Cr of 1.78. Fig. 4 shows the X-ray pattern of LDH–CS. Although
this material reveals to be amorphous, however it reveals a layered
structure (Radha and Vishnu Kamath, 2004). In fact, the basal spac-
ð9Þ ing, d003, which represents the thickness of a layer plus the inter-
layer space, was 7.60 Å, while the d006, which represents the
shortest distance between two cations of the layer was 3.93 Å.
During the formation of LDHs a fraction of divalent cations are
substituted by trivalent and consequently the layers acquire a po-
ð10Þ
sitive charge which is neutralized by a counterion, as carbonate,
which is intercalated in the interlayer region. This causes an in-
crease in the interlayer spacing from 4.77 Å of Mg(OH)2 to a higher
value, 7.6 Å, seen in the LDHs.

Please cite this article in press as: De Martino, A., et al. Sustainable sorption strategies for removing Cr3+ from tannery process wastewater. Chemosphere
(2013), http://dx.doi.org/10.1016/j.chemosphere.2013.03.051
6 A. De Martino et al. / Chemosphere xxx (2013) xxx–xxx
Fig. 4. X-ray of LDH of magnesium and chromium obtained by using commercial
salt (LDH–CS) and tannery process wastewater (LDH–TPW=LDH–Mg–Cr) as starting
material.
As observed in Fig. 4, the diffratogram of LDH–TPW shows the
same pattern as LDH–CS but with little differences in d003
(7.83 Å) and d006 (3.88 Å). This small increase in the average basal
spacing indicates an intercalation of small anionic groups in-be-
tween the brucite-like sheets of the LDH. The chemical analysis
of the supernatant obtained after the preparation of LDH–TPW
evidences a Cr3+ removal corresponding to 99.9% and a decreasing
of COD from 13.17 g L1 to 8.70 g L1. In fact, the COD removal
depends on both its concentration in TPW and type of the organic
load. Clearly, a high value of COD causes a low percentage of
removal as consequence of the saturation of the matrix.
4. Conclusions
The use of LDH–HP allows to reduce the polluting load of TPW
by (i) anionic exchange and complexation of Cr3+ with the func-
tional group (ACOO and AOH) of the sorbent, (ii) anionic ex-
change of CO23 with Cl and SO2
4 and (iii) brake down the COD
values. The basilar advantage of LDH–HP with respect to the free
LDH is a much more stability of the complex.
The production of LDH–TPW using Cr3+ natively occurring in
TPW allows to achieve three fundamental advantages: (i) the al-
most complete removal of Cr3+ from TPW, (ii) the reduction of
COD; and (iii) the recycling of the resulting complex for other
applications.
However, further studies are necessary to replace carbonate
ions chosen for this study with the anions natively present in
TPW, with the final objective to exploit this last strategy for a more
complete purification of TPW.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemosphere.
2013.03.051.
Please cite this article in press as: De Martino, A., et al. Sustainable sorption strategies for removing Cr3+ from tannery process wastewater. Chemosphere
(2013), http://dx.doi.org/10.1016/j.chemosphere.2013.03.051
References
Anirudhan, T.S., Suchithra, P.S., 2008. Synthesis and characterization of tannin-
immobilized hydrotalcite as a potential adsorbent of heavy metal ions in
effluent treatments. Appl. Clay Sci. 42, 214–223.
APHA, Wef, AWWA, 1998. In: Clesceri, L.S., Greenberg, A.E., Eaton, A.D. (Eds.),
Standard Methods for the Examination of Water and Wastewater, 20th ed.
American Public Health Association, Washington, DC, USA.
Barriga, C., Gaiten, M., Pavlovic, I., Ulibarri, M.A., Hermosin, M.C., Cornejo, J., 2002.
Hydrotalcite as adsorbent for 2,4,6 trinitrophenol: Influence of the layer
composition and interlayer anions. J. Mater. Chem. 12, 1027–1032.
Capasso, R., De Martino, A., Arienzo, M., 2002. Recovery and characterization of the
metal polymeric organic fraction (polymerin) from olive oil mill wastewaters. J.
Agric. Food Chem. 50, 2846–2855.
Capasso, R., Pigna, M., De Martino, A., Pucci, M., Sannino, F., Violante, A., 2004.
Potential remediation of waters contaminated with Cr (III), Cu and Zn by
sorption on the organic polymeric fraction of olive mill wastewater (polymerin)
and its derivatives. Environ. Sci. Technol. 38, 5170–5176.
Da Fonseca, M.G., De Oliveira, M.M., Arakaki, L.N.H., 2006. Removal of cadmium,
zinc, manganese and chromium cations from aqueous solution by a clay
mineral. J. Hazard. Mater. B137, 288–292.
Delgado, R.R., Vidaurre, M.A., De Pauli, C.P., Ulibarri, M.A., Avena, M.J., 2004. Surface-
charging behavior of Zn–Cr layered double hydroxide. J. Colloid Interface Sci.
280, 431–441.
Giles, C.H., Smith, D., Huitson, A., 1974. A general treatment and classification of the
solute adsorption isotherms. I. Theor. J. Colloid Interface Sci. 47, 755–765.
Goh, K.H., Lim, T.T., Dong, Z., 2008. Application of layered double hydroxides for
removal of oxyanions: a review. Water Res. 42, 1343–1368.
Ho, Y., McKay, G., 1999. Pseudo-second order model for adsorption system. Process
Biochem. 34, 451–465.
Iorio, M⁄., De Martino, A., Violante, A., Pigma, M., Capasso, R., 2010. Synthesis,
characterization, and sorption capacity of layered double hydroxides and their
complexes with polymerin. J. Agric. Food Chem. 58, 5523–5530.
Leroux, F., Adachi-Pagano, M., Intissar, M., Chauvière, S., Forano, C., Besse, J.P., 2001.
Delamination and restacking of layered double hydroxides. J. Mater. Chem. 11,
105–112.
Lv, L., He, J., Wei, M., Evans, D.G., Duan, X., 2006. Uptake of chloride ion from
aqueous solution by calcined layered double hydroxides: equilibrium and
kinetic studies. Water Res. 40, 735–743.
Namasivayama, C., Yamuna, R.T., 1995. Adsorption of chromium (VI) by a low-cost
adsorbent: biogas residual slurry. Chemosphere 30, 561–578.
Pavlovic, I., Ulibarri, M.A., Hermosin, M.C., Cornejo, J., 1997. Sorption of an anionic
surfactant from water by a calcined hydrotalcite-like sorbent. Fresenius
Environ. Bull. 6, 266–271.
Pavlovic, I., Barriga, C., Hermosin, M.C., Cornejo, J., Ulibarri, M.A., 2005. Adsorption
of acidic pesticides 2,4-D, clopyratid and picloram on calcined hydrotalcite.
Appl. Clay Sci. 30, 125–133.
Pavlovic, I., Pérez, M.R., Barriga, C., Ulibarri, M.A., 2008. Adsorption of Cu2+, Cd2+ and
Pb2+ ions by layered double hydroxides intercalated with the chelating agents
diethylenetriaminepentaacetate and meso-2,3-dimercaptosuccinate. Appl. Clay
Sci. 43, 125–129.
Perez, M.R., Pavlovic, I., Barriga, C., Cornejo, J., Hermosín, M.C., Ulibarri, M.A., 2006.
Uptake of Cu2+, Cd2+ and Pb2+ on Zn–Al layered double hydroxide intercalated
with edta. Appl. Clay Sci. 32, 245–251.
Radha, A.V., Vishnu Kamath, P., 2004. Oxidative leaching of chromium from layered
double hydroxides: mechanistic studies. Bull. Mater. Sci. 27, 355–360.
Sannino, F., Iorio, M., De Martino, A., Pucci, M., Brown, C.D., Capasso, R., 2008.
Remediation of waters contaminated with ionic herbicides by sorption on
polymerin. Water Res. 42, 643–652.
Ulibarri, M.A., Hermosin, M.C., 2001. Layered Double Hydroxides: Present and
Future. Nova Science Publishers, Inc., New York. 253.
Ulibarri, M.A., Pavlovic, I., Barriga, C., Hermosin, M.C., Cornejo, J., 2001. Adsorption
of anionic species on hydrotalcite-like compounds:effect of interlayer anion and
crystallinity. Appl. Clay Sci. 18, 17–27.
Vadivelan, V., Vasanth Kumar, K., 2005. Equilibrium, kinetics, mechanism, and
process design for the sorption of methylene blue onto rice husk. J. Colloid
Interface Sci. 286, 90–100.
Weber, W.J., Morris, J.C., 1963. Kinetics of adsorption on carbon from solution. J.
Sanit. Eng. Div. ASCE 89, 31–59.
Wu, D., Sui, Y., He, S., Wang, X., Li, C., Kong, H., 2008. Removal of trivalent chromium
from aqueous solution by zeolite synthesized from coal fly ash. J. Hazard. Mater.
155, 415–423.