International Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 15 No: 02 21

Characterization and Use of Noni (Morinda citrifolia

L.) Seeds for the Removal of Hexavalent Chromium
Ions from Aqueous Solutions
Caroline de G. Sampaio1,3, Flvio A. de Freitas 2,5, Francisco T. C. de Souza2, Edy S. de Brito4, Helena Becker2,
Maria T. S. Trevisan1
1
Departament of Organic and Inorganic Chemistry, Federal University of Cear - Fortaleza, Cear, Brazil
2
Departament of Analytical and Physical Chemistry, Federal University of Cear -
Fortaleza, Cear, Brazil
3
Federal Institute of Cear, Fortaleza, Cear, Brazil
4
Embrapa Tropical Agroindustry, Fortaleza, Cear, Brazil
5
Institute of Chemistry - Federal University of Rio de Janeiro, Rio de Janeiro - RJ Brazil
* Corresponding author. Tel: +55 85 33669981; fax: +55 85 88090767
E-mail address: carol-quimica@hotmail.com (Caroline de Goes Sampaio)

Abstract-- In this present study, the adsorption of hexavalent
chromium (Cr(VI)) ions from synthetic aqueous solution was
investigated using noni seeds (NS). The biosorbent was
characterized using FTIR, X-ray fluorescence, BET, TGA and
DSC techniques, PZC, superficial groups and organic matter
content. The effect of various process parameters such as the
initial pH, adsorbent dosage, initial concentration of Cr(VI), the
reduction of Cr(VI) to Cr(III) and contact time has been studied
in batch-stirred experiments. Maximum removal of Cr(VI) ions
in aqueous solution was observed at pH 1.0 for NS. The removal
efficiency of Cr(VI) ions from the aqueous solution was found to
be 100% for initial metal ion concentration of 10 mg L-1. Various
isotherm models were studied and the distribution coefficient
show that the adsorption could be described by Langmuir
isotherm model which maximum adsorption capacity of 7.94 mg
g-1. The pseudo-second-order kinetic of the adsorption process
was validated with experimental data. The results indicate that
noni seeds proved to be a promising adsorbent for the removal of
Cr(VI) ions from aqueous solution.
Index Term-- chromium (VI), adsorption, reduction, noni,
seeds.
1. INTRODUCTION
Water is a natural essential resource for humanity,
but has been affected by human activities. The waste and
industrial effluents are largely responsible by contamination
through the release of pollutants materials such as toxic metals
and high concentration of organic matter. These substances
change the physical and chemical characteristics of the water
and causes problems in the biota.
Chromium is a metal primarily derived from
chemical processing, manufacturing stainless steel,
electroplating, leather and pigments [1-2]. This metal have
various forms of oxidation ranging from -IV to + VI
prevailing in nature in forms of hexavalent (Cr(VI)) and
trivalent (Cr(III)) chromium. The Cr(VI) is found in
oxyanions form (HCrO4-, CrO42- and Cr2O72-), which are water
soluble and can be easily transported, polluting a large stretch
of water resources [1-3].
Trace amounts of Cr(III) is essential for plants and
animals, however the Cr(VI) is toxic [1, 3] and can cause skin
irritations, liver problems, difficult in respiratory system and
development of cancer [3-9]. Thus, the Cr(VI) removed by
adsorption or reduced to Cr(III) can be evaluated as beneficial
effects on the environment [10].
The most usual methods of wastewater treatment for
removal of hexavalent chromium, as well as other metals are
ion exchange, ultrafiltration, process membrane
(electrodialysis and reverse osmosis), precipitation, reduction
and adsorption or bioadsorption [7-8, 11].
The bioadsorption is an important technique because
it combines low cost with good removal efficiency, as well as
being less aggressive to the environment in wastewater
treatment [3, 12]. The use of low cost materials for used as
bioadsorvents to Cr(VI) remove in waste of industrial water
[7], among these materials include: coconut shells [13];
sawdust [14]; sugar cane bagasse [15]; wool [16] and wheat
bran [17], among others [18]. Many of these residues have no
application and they are rejected by the industry. When used,
they are in small amounts or utilized wrongly, becoming an
environmental problem.
Morinda citrifolia L. is a tropical plant of the
Rubiaceae family, it also is known as noni [19]. Ancient
people used noni fruits as food, medicine and source of colors
to paint clothes [20]. There are very old reports of the use of
the plant for the treatment of cancer, infections, arthritis,
diabetes, asthma, hypertension, and other diseases and pain
[21].
The fruit is known for a long time and has been
studied extensively to check their toxicity and their properties.
Approximately 160 phytochemical compounds have been
identified from the noni plant, and most of the nutrients are
phenolic compounds, organic acids and alkaloids [22].

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 International Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 15 No: 02
Noni industry has greatly increased in the last 10
years, with the great marketing world made on the juice,
especially after the approval of the juice as non-toxic and
healthy food by the European Union [23].
The dry seeds represent about 2.5% of the total
weight of the fruit and these seeds are rejected without any use
[24]. In French Polynesia, one of the countries that use the
noni, the waste of seed was more than 150 tons [25].
This work aims to evaluate the Cr(VI) removal study
by noni seeds (NS), obtaining information on the isotherm and
adsorption kinetics, chemical and physical characterization of
this seed.
2. EXPERIMENTAL
2.1. Materials
All reagents used in the experiments were of
analytical grade and they were used in purified milli-Q water
system to prepare solutions. The 1,5-Diphenylcarbazide
necessary for the colorimetric assay to quantify Cr(VI) was
from Sigma-Aldrich. A stock solution of 1000 mg L-1 of Cr
(VI) was prepared using K2Cr2O7 (Merck). NaOH and HCl
solutions (Vetec) were prepared to correct the pH of the
solutions during the experiments.
2.2. Obtained and treatment of noni seeds (NS)
The NS were provided by EMBRAPA (Brazilian
Agricultural Research Corporation). The plant was identified
by department of Biology, Federal University of Cear (UFC),
and a voucher specimen (n 44,566) was deposed in the
Herbarium Prisco Bezerra, of the UFC, Cear, Brazil. This
material was triturated, washed with milli-Q water system,
dried at 60 C (48 h) and sieved through standard sieves to
obtain a particle size of 25 mesh. They were stored at ambient
temperature.
2.3. Instrumentation
The instruments used for data collection and
characterization of adsorbent were (i) pH meter (WTW, 3310)
for the solutions pH adjustment, (ii) X-ray Fluorescence
(Rigaku, ZSX Mini II) for the analysis of the minerals present
in the ash, (iii) analysis of the signals by using Fourier
transform infrared spectrometer (FTIR) (Perkin Elmer,
Spectrum 1000), in the range 4000-400 cm-1, (iv)
spectrophotometer UV-vis (Varian, 1E) for colorimetric
analysis of Cr(VI), (v) atomic absorption (Varian, AA 240 FS)
for total chromium (Cr(TOTAL)) analysis (vi) BET analyse
(Quantachrome instruments, ASAP 2020 V3.01 G), using N2
adsorption/desorption isotherms at 77 K (vii)
Thermogravimetric analyse were performed by DSC
(Shimadzu, DSC-50) and TGA (Shimadzu, TGA-50
Thermobalance).
2.4. Chemical characterization of the NS surface compounds
The determination of acidic and basic groups in the
NS surfaces were by Boehm titration method [26-27] in which
NaHCO3 (0.1 mol L-1), Na2CO3 (0.05 mol L-1), NaOH (0.02
and 0.1 mol L-1) and HC1 (0.02 mol L-1) solution were
155102-4848-IJCEE-IJENS April 2015 IJENS
22
prepared using milli-Q water. 20 mL of these solutions were
added to flasks containing 200 mg of seed. These samples
were shaken during 24 hours and the seeds were separated
from solution by decantation and filtration. The excess of acid
or base was determined by back titration using hydrochloric
acid (0.02 and 0.1 mol L-1) and sodium hydroxide (0.02 mol L-
1
) solution. The point of zero charge (PZC) of NS was
determined using NaNO3 solution [26]. The pH of each
solution was then measured using a digital pH meter. The PZC
was determined as the pH value to converge as a function of
pH biosorbent mass. Quantitative analysis of the organic
matter was performed by heating the organic material. The
gravimetric method was used where the seed was heated at
550 C for 1 h. Ash obtained were analysed in ray
fluorescence X.
2.5. Cr (VI) removing assays
The effect of pH on the removal of Cr(VI) was
studied using 50 mL of a 10 mg L-1 of Cr(VI) and 0.5g of NS.
Different volumes of 0.1 mol L-1 HCl or 0.1 mol L-1 NaOH
were added to adjust the pH of the mixture (pH 1 - 9) and
contact time of 120 min. For varying the concentration NS
were weighed masses ranging from 0.1 - 0.5 g maintaining the
concentration of 10 mg L-1 of Cr(VI), pH 1 and contact time
of 120 min. The equilibrium study adsorption isotherm was
performed at room temperature (25 1 C). Removal of
Cr(VI) from aqueous solution using NS was performed using
50 mL solution of Cr(VI) initial concentration in the range 1 -
50 mg L-1, NS dosage was 0.2 g and pH 1. To observe the
influence of NS contact time with Cr (VI) and Cr(TOTAL)
removal, it was set 0.5 g of dosage and 50 mg L-1 Cr(VI). For
this study, it was observed the change that the pH may suffer
from contact with the chromium solution, as well as the
relationship between species of Cr (VI) and Cr (III). All
experiments took place under stirring at 120 rpm. Samples
were collected and quantified for determining the remaining
residual concentration in solution.
The concentration of Cr(VI) in solution was
determined by spectrophotometry with 1,5-diphenylcarbazide
at 540 nm [28]. Each assay was performed in duplicate.
Cr(TOTAL) was determined by atomic absorption spectroscopy
(AA) after the adsorption test. The reduction of Cr(III) was
calculated from the difference between the Cr(TOTAL) and
Cr(VI) in solution. The percentage removal of Cr(VI) was
calculated for each test using the equation 1:
( ) ( )
where Ci and Cf are the initial and final concentrations of the
metal in mg L-1,respectively. The adsorption capacity (q e) of
biosorbent was calculated from the equation 2:
( ) ( )
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where Ci and Cf are the initial and final concentrations of
metal in mg L-1, respectively.
V is the solution volume (L) and m is weight (g) of the
adsorbent used in the experiment [29].
3. RESULTS AND DISCUSSION
3.1 Characterization of the NS
In order to understand the Cr(VI) removal processes
using NS, it is necessary to know the physical and chemical
characteristics of the adsorbent material, which can be seen in
Table 1. The BET surface area and pore single point full
adsorption volume of NS were found to be 11.13 m2 g-1 and
0.026 cm3 g-1, respectively. Average pore width of the
composites was obtained to be 93.77 . These values are
similar to other biosorbents cited in the literature [30-32].
The NS has a high amount of lactonic, phenolic and
carbonyl groups (table 1), these groups are responsible for
much of the removal of metals, especially for surface
complexation [33]. PZC value found for seeds was 5.31. This
means that for the removed of Cr(VI), which is in the form of
anion (Cr2O72-, CrO4-2, HCrO4-) must use solutions with pH
lower than the PZC. Thus hydroxyls phenolics (-OH) present
in the adsorbent surface groups will be protonated (-OH2+),
promoting the adsorption of negatively charged species [34].
The organic matter content of the noni seeds was
98.14%. The ash components were analysed by X-ray
fluorescence. The data on the different elements detected in
NS are listed in Table 1. It is possible to note that the major
constituents of NS are calcium and potassium.
The IR spectral bands (Table 2) were observed
signals at 3420 cm-1 characteristic stretching of C- OH linked
phenolic groups. The regions between 1750 and 1600 cm-1 are
characteristic for carbonyl groups. It was observed an intense
band at 1644 cm-1, characteristic of C = O of carbonyl groups
[35]. All these results confirm the data obtained from the
measurement of surface groups by Boehm titration method.
Furthermore, the axial deformation vibration of C-O bond,
which appears at 1232 cm-1 region may suggest the presence
of esters or lactones attached to aromatic groups [17].
The results of thermogravimetric analyse (TGA) for
NS are presented in Figure 1 and were observed by TGA mass
loss of two major bands. The first, with a mass variation of 9
% between 30 - 100 C, is associated to water adsorbed to the
material. Moisture elimination was observed by DSC profile
that this is an endothermic event. The second temperature
range between 250 and 400 C, there is a greater loss of
weight, approximately 60%, which can be attributed to the
breakdown of the hemicellulose, the cellulose breaking links
and phenolics compounds, which features an exothermic event
in the DSC curve. The thermal behaviour presented by NS is
similar to the main natural source materials used industrially
developing new materials from biomass [36].
3.2. Chromium hexavalent removal studies
3.2.1 Effect of pH on the removal of Cr (VI)
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The acidity of the solution is an important parameter
in the process of Cr(VI) removal. The results are presented in
Figure 2 and the optimum pH for maximum removal of Cr(VI)
was founded 1.0 for NS (100%). Different mechanisms has
been proposed for the interaction of Cr(VI) and the adsorbent
such as: electrostatic attraction, chelation, complexation,
chemisorption and reduction of Cr(VI) reaction on the surface
[17].
There are different anionic species to Cr(VI) ions in
aqueous solution, depending on the pH value (HCrO4-, CrO42-,
Cr2O72-) or molecular (H2CrO4). The HCrO4- is the dominant
species in pH 1 [16-18] and was the predominant specie in this
study.
The PZC (5.31) directs that at pH below this value
will better removal of anionic species. In pH above the PZC it
will form a network of negative charges on the surface of
biosorbent, which it will cause repulsion of hexavalent
chromium anions.
It is important assess the pH value during the removal
test, because in lower pH (pH <1) the H2CrO4 specie is the
predominance form of Cr(VI), disfavouring the adsorption
process [37-38]. In order to ensure only the presence of
anionic species, the pH of the solution was monitored during
the experiment and it was observed no change at pH
throughout the assay.
3.2.2. Effect of dose of NS
Table 2 shows the percentage of Cr(VI) removed
when the changed seed mass. Through this analysis it was
found that the minimum mass needed for removal of 10mg L -1
Cr (VI) is 0.2g. Most studies reported in the literature for the
removal of Cr (VI) using a mass greater than 1.0 g of sorbent
in a similar volume of the chromium solution [16, 27, 39-40].
Study involved used various adsorbents (tamarindus seed,
coconut shells, peanut, and walnut) for the adsorption of
Cr(VI) 10 mg L-1 and was used 2g of adsorbent did not exceed
80% at a contact time of 3 h [39].
3.2.3. Effect of initial concentration of Cr (VI)
The Cr (VI) concentration was varied in order to
determine the removal capacity (q), keeping pH 1, the mass of
0.2g of NS and 90 minutes of contact time. Table 4 shows that
the removal percentage of Cr (VI) was 66.46 % in 50 mg.L-1,
indicating removal of Cr (VI) equivalent to 33.23 mg L-1. The
removal capacity of Cr (VI) increases with increasing metal
concentration, but more Cr(VI) remained in solution at high
concentrations of metals due to saturation of the binding sites
at NS.
The relationship between amount of metal ions
adsorbed onto the surface of the biosorbent at a constant
temperature and its concentration in the equilibrium solution is
referred to as adsorption isotherm. These isotherms are useful
to estimate the total amount of adsorbent needed to adsorb a
required amount of adsorbate solution [41]. In this study, the
observed equilibrium data for the ions of Cr(VI) in the NS
have been explained by the following thee isotherms, namely
Langmuir, Freundlich and Temkin (Figure 3). The best fit for
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each isotherm model was evaluated in terms of the distribution
coefficient (R2).
Langmuir isotherm
The linear form of the Langmuir is expressed by the
equation 3 and takes the following form [42]:
( )
where Ce is the equilibrium concentration of the metal, q e is
the adsorption capacity at equilibrium, Q0 is the maximum
monolayer adsorption and b is a constant which relates the
reaction rate.
Another essential feature of the Langmuir model can
be expressed in terms of constant separation factor of the
balance dimension less parameter, RL [43], defined as
(equation 4):
( )
where C0 is the initial concentration of Cr(VI) ions and the
value of the separation factor is a measure of sorption
behaviour. If RL>1 the sorption is unfavorable, RL=1 the
Langmuir isotherm is linear, RL=0 irreversible. When 0<RL<1
the sorption process is favourable.
From the experimental results the Langmuir model
isotherm fits quite well with the experimental data
(distribution coefficient, R2 = 0.95) at room temperature (25
C). The removal of Cr(VI) is favorable because of value R L
(0<RL<1). The adsorption involves the formation of a
monolayer Cr(VI) in NS surface. The values given in Table 5
indicate that the Langmuir model was suitable for balance and
isotherm fits for the removal of Cr(VI). Maximum Cr (VI)
adsorption capacity was 7.94 mg g-1 for NS (Table 5).
Freundlich isotherm
The linear form of the Freundlich is expressed by the
equation 5 and the model proposes an adsorption multilayer
and the isotherm adsorption equation can be written as [44]:
( )
where Kf is a constant related to the Freundlich adsorption
capacity (L mg-1) and n represents the heterogeneous factor
related to the intensity of adsorption of the Cr(VI) and NS,
where 1/n=0 reversible, 1/n<0 unfavorable, 1/n>0 favorable
sorption.
Temkin isotherm
The Temkin isotherm model contains a factor that
takes into account specifically only the adsorbent-adsorbate
interactions, by neglecting the low and high concentration
values, and it is assumed that the decrease in sorption heat is
linear rather than logarithmic, implied in the Freundlich
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equation [45]. The linearized form of the Temkin equation 6 is
expressed by the following equation:
( )
where R is the universal gas constant (8.314 J mol-1 K-1), T is
the temperature (in Kelvin), bt represents the isothermal
constants Temkin (J mol-1) and At is the isotherm binding
constant Temkin balance (L mg-1). The values of bt and At
were determined from the slope and intercept point obtained
by curve between qe and lnCe.
Table 6 presents a comparison of the adsorption
capacity of the ion Cr(VI) on different biosorbents reported in
the literature. There are several factors that can alter the
adsorption capacity of an adsorbent, such as structural
variations and surface functional groups, size of surface area,
porosity and pH of the solution [46].
3.3. Ratio Cr (VI) and Cr (III): metal reduction process
indication and kinetics of adsorption and reduction
In the adsorption process of chromium hexavalent the
metal may be reduced at low pH, in which Cr(IV) is converted
to Cr(III) and the determination of the metal reduction is an
important parameter, given that not all the Cr(VI) is removed
by adsorption [47].
According to results shown in Figure 4, was observed
that the removing kinetics of Cr(VI) and Cr (TOTAL) is fast
during the 10 min, because the process mainly occurs in the
outer surface of NS. Then a slow phase (10 - 30 min) occurs in
inner surface of NS. In these instants, the Cr(VI) concentration
decreases considerably when compared to the Cr (TOTAL). This
process can be explained due of reducing the Cr(VI) to Cr(III)
by surface groups (phenols and carbonyls). After 30 min., a
constancy in the concentration of Cr(TOTAL) determines that the
adsorption equilibrium was reached but the reduction is still.
The results indicates that initially prevailed removal
by adsorption of Cr(VI) and later by metal reduction (Cr(VI)
to Cr (III) after 10 min of contact time). This reduction can be
induced by influence of acid pH and can occur on the surface
of the adsorbent or the solution by substances from the
biomaterial [47 49].
The reduction may occur under the influence of
tannins and phenolic compounds, substances that are present
in the NS because of their chemical characterization of surface
groups [50], and also because the substance which is the
material such as americanin A [51] which is a phenol having a
good oxidation potential [52], may further reduce the Cr (VI)
to Cr (III). The percentage removal of Cr (TOTAL) in peanut
hulls, wood and orange peel sheet similar to the percentage
found in this study (approximately 40%) [47].
3.3.1 Adsorption kinetics
Kinetic studies are important in determining the
adsorption rate and describe the solute gain rate, which affects
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the endurance time in the adsorption process. In this study,
two kinetic models, which model pseudo-first order and
pseudo-second-order, were tested to predict the adsorption
data of the ions Cr(VI) NS versus time. The adsorption
kinetics are expressed by the amount of surface adsorbed
metal at equilibrium q (mg g-1) and the adequacy of the model
is evaluated according to the values of the distribution
coefficient R2. The kinetic model pseudo-first-order was
proposed by Lagergren [53] and is expressed by the following
equation 7:
( ) ( )
where k1 is the rate constant (min-1) qe and qt are the amount
of Cr(VI) adsorbed on the surface of seeds at equilibrium (mg
g-1) and time t (min.), respectively. Is the plotted graph of ln
(qe-qt) against time, and k1 and q values were determined by
the slope of the straight line and the values of the y-axis
intercepts, according to the graph shown in Figure 5.
According to the kinetic model pseudo-second-order,
the occupation rate of adsorption sites is proportional to the
square numbers of unoccupied sites [54]. It is expressed by the
following equation 8:
( )
where k2 (g mg-1 min-1) is the rate constant was determined by
graphic t/qt vs.time (Figure 6). The constants of the pseudo-
first-order and pseudo-second-order, the calculated q values
and the corresponding values of the regression coefficients are
shown in Table 7.
The value of the distribution coefficient (R2) for the
kinetics models of removing of Cr(VI) showed the better
adjusted to the kinetics of pseudo-second order, as can see the
difference between the distribution coefficient of the two
models, in which this value was 0.991 for the kinetic pseudo-
second order. The estimated value of q e agreed with the
experimental values (3.08 mg g-1), indicating that the rate-
limiting step is the chemical adsorption of the ions Cr (VI) and
NS. However, both kinetic models do not explain the exact
mechanism of adsorption which occurs in the biosorption
process. However, it can be explained by intraparticle
diffusion model which describes the mechanism of diffusion
on the surface of the biosorbent [55] and is given by the
following equation 9 - 10:
( )
( )
-1 0,5
where kf is the intraparticle diffusion constant (mg g min )
and C is a constant that gives an idea about the thickness of
the boundary layer, which can be calculated by means of the
graph between qT and t0.5 and may be observed in Table 7.
The overall biosorption mechanism can be
represented by three steps: (a) External diffusion, in which the
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25
occurs in which the transport of the adsorbate to the outer
surface of the adsorbent occurs, (b) intraparticle diffusion,
which occurs the transportation of the adsorbate in the pores
of the adsorbent and (c) the inner biosorption rate sites. The
mass transfer Cr (VI) to the surface and within the NS pores
determines the rate limiting steps.
Through Figure 7 it can be seen that the biosorption
process was followed in only one region and it is clear that
there is no adsorbate diffusion boundary layer in the initial
stage, while later, the linear portion describes the intraparticle
diffusion. The slope of the line and the y-axis point of
intersection of the second linear portion of the graph represent
the intraparticle diffusion rate (Kf) and effects in the boundary
layer (C), respectively. The speed limiting factor is the rate of
adsorption on the surface, and is directly dependent on the
intersection of axis y value (C). The calculated values of
intraparticle diffusion are shown in Table 7, where it can be
seen that Kf was 0.230.
4. CONCLUSION
Natural organic materials of low cost have been used
with alternative adsorbents for the removal of metals from
aqueous solutions. NS have been studied with respect to
chemical and textural properties. The characterization of NS
showed high amount of phenolic and carbonyl groups
confirmed by FTIR and Boehm method, the X-ray
fluorescence showed major constituents of NS are calcium and
potassium. The adsorption of Cr(VI) using NS was
investigated by changing many parameters during the
experiment. The initial Cr(VI) amount in the solution phase
and the pH value of bulk solution influenced the adsorption
quantity. The optimum pH for the removal of Cr(VI) by NS
was 1.0 at the equilibrium conditions. The maximum uptake
of Cr(VI) percentages was obtained as 100% when metal
concentration was 10 mg L-1. The adsorption value of
chromium was related to contact time and attained to the
equilibrium at 30 min for Cr(TOTAL). Data isotherm of Cr(VI)
adsorption on NS was modelled by Langmuir adsorption
model and NS has maximum adsorption capacity of 7.94 mg
g-1 of Cr(VI) from the aqueous solution. When amount of
adsorbent increased in the solution phase, the retention of
Cr(VI) increased in the solid phase. The pseudo-second-order
kinetic of the adsorption process was validated with
experimental data. The results indicate that noni seeds was
shown to be a promising adsorbent for the removal of Cr(VI)
ions from aqueous solution.
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Table I
Chemical and physical characterization (BET, surface groups and elements) in NS
27
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Pore volume 0.026 cm3 g1

Pore diameter 93.77
Surface area (BET) 11.13 m2 g1
Organic material 98.14 (wt %)
Surface groups mol g-1
Carbonyl groups 12.00 0.04
Phenolic groups 37.00 0.14
lactonic groups 177.00 3.10
Basic groups 202.00 6.80
Elements %m/m
Ca 42.24
K 27.72
P 9.89
Al 6.53
Si 5.87
S 5.38
Cl 2.36

Table II
Assignment of bands in FTIR for encapsulated mangiferin systems [17, 35].

NS (cm-1) Assignment
3420 C-OH of phenolics compounds
1643 C=O of carbonyl groups
1590 C=C aromatic ring stretching
1459 Methylene C-H bending
1232 C-O stretch of carboxilic acids
1039 Vibration involving C-O

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Table III
Effect of NS dosage on the biosorption of Cr(VI) ions
Mass (g) Removal efficiency (%)
0.1 77.50
0.2 100
0.3 100
0.4 100
0.5 100

Table IV
Effect of initial metal ion concentration adsorption onto the NS
Initial conc. of Cr(VI) Removal efficiency
(mg L-1) (%)
1 100.00
10 100.00
25 88.71
30 69.68
50 66.46

Table V
Isotherm model constants and distribution coefficient (R2) for the biosorption of Cr(VI) ions onto the NS.
Isotherm Models Parameters Cr(VI)
Langmuir Q0 (mg g-1) 7.94
b (L mg-1) 1.25

R2 0.95
RL 8.3x10-2 1.8x10-3
Freundlich Kf (L mg-1) 2.88
n (g/L) 2.68

R2 0.85
Temkin At (L mg-1) 0.38
bt (J mol-1) 6.63

R2 0.48
Table VI
Comparison of the adsorption capacity (Q0) of Cr(VI) some agroindustrial waste.
Biosorvent Q0 (mg g-1) Reference
Noni seeds 7.94 This work
Wheat bran 4.53 [17]
Jatropha oil cake (DJOC) 131.57 [34]
Modified riverbed sand 0.79 [38]
Shells of almonds 3.40 [3]
Tamarindus indica 90 [39]
Hazelnut shells 170 [29]

Table VII
Kinetic constants for the biosorption of Cr(VI) onto the NS.
Pseudo-primeira ordem Pseudo-segunda ordem Intraparticle diffusion
Temp K1 (min-1) qe R2 K2 qe R2 Kf R2
-1 -1 -1 -1 -1 0.5
(C) (mg g ) (g mg min ) (mg g ) (mg g min )
25 0.040 2.880 0.984 0.014 3.111 0.991 0.230 0.834

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100

80

weight %
60

40

20

0
0 200 400 600 800 1000
Temperature (C)

Fig. 1. Thermogravimetric curve for NS using 10 mg of sample with a heating rate of 10 C min-1 under a nitrogen flow of 50 mL min-1.

100

95
Removal Efficiency (%)

90

85

80

75

70

65
0 1 2 3 4 5 6 7 8 9 10
pH

Fig. 2. Effect of pH of the solution to study the removal of chromium (VI) by NS (Conditions: pH variety 1-9; initial concentration of Cr(VI) 10 mg L-1; amount
of adsorbent. 0.5 g; volume of adsorption medium = 50 mL; temperature. 25 1 C; stirring rate 120 rpm).

6
q (mg g )
-1

0
0 2 4 6 8 10 12 14 16 18
-1
Ce (mg g )

Fig. 3. Adsorption isotherms of Cr(VI) on NS (Conditions: initial concentration of Cr(VI). 1 50 mg L-1; amount of adsorbent. ; pH 1. 0.2 g; volume of adsorption
medium. 50 mL; temperature. 25 1 C; stirring rate 120 rpm).

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50
Cr(VI)
Cr(TOTAL)

Chromium concentration (mg L )

40

-1
Cr(III)

30

20

10

0 50 100 150 200 250

time (min)

Fig. 4. Variation of the concentration of Cr (VI) and Cr (III) in function of time: adsorption and reduction process.

0,6

0,4

0,2

0,0

-0,2
Log (qe-qt)

-0,4

-0,6

-0,8

-1,0

-1,2

-1,4
0 20 40 60 80 100
Time (min)

Fig. 5. Kinetic model pseudo-first order for NS.

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80

70

60

50

40

t/qt 30

20

10

0
0 50 100 150 200 250
Time (min)

Fig. 6. Kinetic model pseudo-second order for NS.

3,0

2,5

2,0
qt (mg/g)

1,5

1,0

0,5

0,0

0 2 4 6 8 10 12 14 16
0,5
t

Fig. 7. Model of Diffusion Intraparticule for NS.

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