Characterization and Use of Noni (Morinda citrifolia L.) Seeds for the Removal of Hexavalent Chromium Ions from Aqueous Solutions
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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, Flávio 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 Ceará - Fortaleza, Ceará, Brazil
2
Departament of Analytical and Physical Chemistry, Federal University of Ceará -
Fortaleza, Ceará, Brazil
3
Federal Institute of Ceará, Fortaleza, Ceará, Brazil
4
Embrapa Tropical Agroindustry, Fortaleza, Ceará, 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 soluble and can be easily transported, polluting a large stretch
chromium (Cr(VI)) ions from synthetic aqueous solution was of water resources [1-3].
investigated using noni seeds (NS). The biosorbent was Trace amounts of Cr(III) is essential for plants and
characterized using FTIR, X-ray fluorescence, BET, TGA and animals, however the Cr(VI) is toxic [1, 3] and can cause skin
DSC techniques, PZC, superficial groups and organic matter irritations, liver problems, difficult in respiratory system and
content. The effect of various process parameters such as the
development of cancer [3-9]. Thus, the Cr(VI) removed by
initial pH, adsorbent dosage, initial concentration of Cr(VI), the
reduction of Cr(VI) to Cr(III) and contact time has been studied adsorption or reduced to Cr(III) can be evaluated as beneficial
in batch-stirred experiments. Maximum removal of Cr(VI) ions effects on the environment [10].
in aqueous solution was observed at pH 1.0 for NS. The removal The most usual methods of wastewater treatment for
efficiency of Cr(VI) ions from the aqueous solution was found to removal of hexavalent chromium, as well as other metals are
be 100% for initial metal ion concentration of 10 mg L-1. Various ion exchange, ultrafiltration, process membrane
isotherm models were studied and the distribution coefficient (electrodialysis and reverse osmosis), precipitation, reduction
show that the adsorption could be described by Langmuir and adsorption or bioadsorption [7-8, 11].
isotherm model which maximum adsorption capacity of 7.94 mg The bioadsorption is an important technique because
g-1. The pseudo-second-order kinetic of the adsorption process
it combines low cost with good removal efficiency, as well as
was validated with experimental data. The results indicate that
noni seeds proved to be a promising adsorbent for the removal of being less aggressive to the environment in wastewater
Cr(VI) ions from aqueous solution. treatment [3, 12]. The use of low cost materials for used as
bioadsorvents to Cr(VI) remove in waste of industrial water
Index Term-- chromium (VI), adsorption, reduction, noni,
[7], among these materials include: coconut shells [13];
seeds. 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,
1. INTRODUCTION
they are in small amounts or utilized wrongly, becoming an
Water is a natural essential resource for humanity,
environmental problem.
but has been affected by human activities. The waste and
Morinda citrifolia L. is a tropical plant of the
industrial effluents are largely responsible by contamination
Rubiaceae family, it also is known as noni [19]. Ancient
through the release of pollutants materials such as toxic metals
people used noni fruits as food, medicine and source of colors
and high concentration of organic matter. These substances
to paint clothes [20]. There are very old reports of the use of
change the physical and chemical characteristics of the water
the plant for the treatment of cancer, infections, arthritis,
and causes problems in the biota.
diabetes, asthma, hypertension, and other diseases and pain
Chromium is a metal primarily derived from
[21].
chemical processing, manufacturing stainless steel,
The fruit is known for a long time and has been
electroplating, leather and pigments [1-2]. This metal have
studied extensively to check their toxicity and their properties.
various forms of oxidation ranging from -IV to + VI
Approximately 160 phytochemical compounds have been
prevailing in nature in forms of hexavalent (Cr(VI)) and
identified from the noni plant, and most of the nutrients are
trivalent (Cr(III)) chromium. The Cr(VI) is found in
phenolic compounds, organic acids and alkaloids [22].
oxyanions form (HCrO4-, CrO42- and Cr2O72-), which are water
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IJENSInternational Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 15 No: 02 22
Noni industry has greatly increased in the last 10 prepared using milli-Q water. 20 mL of these solutions were
years, with the great marketing world made on the juice, added to flasks containing 200 mg of seed. These samples
especially after the approval of the juice as non-toxic and were shaken during 24 hours and the seeds were separated
healthy food by the European Union [23]. from solution by decantation and filtration. The excess of acid
The dry seeds represent about 2.5% of the total or base was determined by back titration using hydrochloric
weight of the fruit and these seeds are rejected without any use acid (0.02 and 0.1 mol L-1) and sodium hydroxide (0.02 mol L-
1
[24]. In French Polynesia, one of the countries that use the ) solution. The point of zero charge (PZC) of NS was
noni, the waste of seed was more than 150 tons [25]. determined using NaNO3 solution [26]. The pH of each
This work aims to evaluate the Cr(VI) removal study solution was then measured using a digital pH meter. The PZC
by noni seeds (NS), obtaining information on the isotherm and was determined as the pH value to converge as a function of
adsorption kinetics, chemical and physical characterization of pH biosorbent mass. Quantitative analysis of the organic
this seed. matter was performed by heating the organic material. The
gravimetric method was used where the seed was heated at
2. EXPERIMENTAL 550 ° C for 1 h. Ash obtained were analysed in ray
2.1. Materials fluorescence X.
All reagents used in the experiments were of
analytical grade and they were used in purified milli-Q water 2.5. Cr (VI) removing assays
system to prepare solutions. The 1,5-Diphenylcarbazide The effect of pH on the removal of Cr(VI) was
necessary for the colorimetric assay to quantify Cr(VI) was studied using 50 mL of a 10 mg L-1 of Cr(VI) and 0.5g of NS.
from Sigma-Aldrich. A stock solution of 1000 mg L-1 of Cr Different volumes of 0.1 mol L-1 HCl or 0.1 mol L-1 NaOH
(VI) was prepared using K2Cr2O7 (Merck). NaOH and HCl were added to adjust the pH of the mixture (pH 1 - 9) and
solutions (Vetec) were prepared to correct the pH of the contact time of 120 min. For varying the concentration NS
solutions during the experiments. 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
2.2. Obtained and treatment of noni seeds (NS) of 120 min. The equilibrium study adsorption isotherm was
The NS were provided by EMBRAPA (Brazilian performed at room temperature (25 ± 1 °C). Removal of
Agricultural Research Corporation). The plant was identified Cr(VI) from aqueous solution using NS was performed using
by department of Biology, Federal University of Ceará (UFC), 50 mL solution of Cr(VI) initial concentration in the range 1 -
and a voucher specimen (n° 44,566) was deposed in the 50 mg L-1, NS dosage was 0.2 g and pH 1. To observe the
Herbarium Prisco Bezerra, of the UFC, Ceará, Brazil. This influence of NS contact time with Cr (VI) and Cr(TOTAL)
material was triturated, washed with milli-Q water system, removal, it was set 0.5 g of dosage and 50 mg L-1 Cr(VI). For
dried at 60 °C (48 h) and sieved through standard sieves to this study, it was observed the change that the pH may suffer
obtain a particle size of 25 mesh. They were stored at ambient from contact with the chromium solution, as well as the
temperature. relationship between species of Cr (VI) and Cr (III). All
experiments took place under stirring at 120 rpm. Samples
2.3. Instrumentation were collected and quantified for determining the remaining
The instruments used for data collection and residual concentration in solution.
characterization of adsorbent were (i) pH meter (WTW, 3310) The concentration of Cr(VI) in solution was
for the solutions pH adjustment, (ii) X-ray Fluorescence determined by spectrophotometry with 1,5-diphenylcarbazide
(Rigaku, ZSX Mini II) for the analysis of the minerals present at 540 nm [28]. Each assay was performed in duplicate.
in the ash, (iii) analysis of the signals by using Fourier Cr(TOTAL) was determined by atomic absorption spectroscopy
transform infrared spectrometer (FTIR) (Perkin Elmer, (AA) after the adsorption test. The reduction of Cr(III) was
Spectrum 1000), in the range 4000-400 cm-1, (iv) calculated from the difference between the Cr(TOTAL) and
spectrophotometer UV-vis (Varian, 1E) for colorimetric Cr(VI) in solution. The percentage removal of Cr(VI) was
analysis of Cr(VI), (v) atomic absorption (Varian, AA 240 FS) calculated for each test using the equation 1:
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 where Ci and Cf are the initial and final concentrations of the
Thermobalance). metal in mg L-1,respectively. The adsorption capacity (q e) of
biosorbent was calculated from the equation 2:
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
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where Ci and Cf are the initial and final concentrations of The acidity of the solution is an important parameter
metal in mg L-1, respectively. in the process of Cr(VI) removal. The results are presented in
V is the solution volume (L) and m is weight (g) of the Figure 2 and the optimum pH for maximum removal of Cr(VI)
adsorbent used in the experiment [29]. was founded 1.0 for NS (100%). Different mechanisms has
been proposed for the interaction of Cr(VI) and the adsorbent
3. RESULTS AND DISCUSSION such as: electrostatic attraction, chelation, complexation,
chemisorption and reduction of Cr(VI) reaction on the surface
3.1 Characterization of the NS [17].
In order to understand the Cr(VI) removal processes There are different anionic species to Cr(VI) ions in
using NS, it is necessary to know the physical and chemical aqueous solution, depending on the pH value (HCrO4-, CrO42-,
characteristics of the adsorbent material, which can be seen in Cr2O72-) or molecular (H2CrO4). The HCrO4- is the dominant
Table 1. The BET surface area and pore single point full species in pH 1 [16-18] and was the predominant specie in this
adsorption volume of NS were found to be 11.13 m2 g-1 and study.
0.026 cm3 g-1, respectively. Average pore width of the The PZC (5.31) directs that at pH below this value
composites was obtained to be 93.77 Å. These values are will better removal of anionic species. In pH above the PZC it
similar to other biosorbents cited in the literature [30-32]. will form a network of negative charges on the surface of
The NS has a high amount of lactonic, phenolic and biosorbent, which it will cause repulsion of hexavalent
carbonyl groups (table 1), these groups are responsible for chromium anions.
much of the removal of metals, especially for surface It is important assess the pH value during the removal
complexation [33]. PZC value found for seeds was 5.31. This test, because in lower pH (pHInternational Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 15 No: 02 24
each isotherm model was evaluated in terms of the distribution equation [45]. The linearized form of the Temkin equation 6 is
coefficient (R2). expressed by the following equation:
Langmuir isotherm
The linear form of the Langmuir is expressed by the ( )
equation 3 and takes the following form [42]:
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
where Ce is the equilibrium concentration of the metal, q e is were determined from the slope and intercept point obtained
the adsorption capacity at equilibrium, Q0 is the maximum by curve between qe and lnCe.
monolayer adsorption and b is a constant which relates the Table 6 presents a comparison of the adsorption
reaction rate. capacity of the ion Cr(VI) on different biosorbents reported in
Another essential feature of the Langmuir model can the literature. There are several factors that can alter the
be expressed in terms of constant separation factor of the adsorption capacity of an adsorbent, such as structural
balance dimension less parameter, RL [43], defined as variations and surface functional groups, size of surface area,
(equation 4): 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
where C0 is the initial concentration of Cr(VI) ions and the
value of the separation factor is a measure of sorption In the adsorption process of chromium hexavalent the
behaviour. If RL>1 the sorption is unfavorable, RL=1 the metal may be reduced at low pH, in which Cr(IV) is converted
Langmuir isotherm is linear, RL=0 irreversible. When 0International Journal of Civil & Environmental Engineering IJCEE-IJENS Vol: 15 No: 02 25
the endurance time in the adsorption process. In this study, occurs in which the transport of the adsorbate to the outer
two kinetic models, which model pseudo-first order and surface of the adsorbent occurs, (b) intraparticle diffusion,
pseudo-second-order, were tested to predict the adsorption which occurs the transportation of the adsorbate in the pores
data of the ions Cr(VI) NS versus time. The adsorption of the adsorbent and (c) the inner biosorption rate sites. The
kinetics are expressed by the amount of surface adsorbed mass transfer Cr (VI) to the surface and within the NS pores
metal at equilibrium q (mg g-1) and the adequacy of the model determines the rate limiting steps.
is evaluated according to the values of the distribution Through Figure 7 it can be seen that the biosorption
coefficient R2. The kinetic model pseudo-first-order was process was followed in only one region and it is clear that
proposed by Lagergren [53] and is expressed by the following there is no adsorbate diffusion boundary layer in the initial
equation 7: 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
where k1 is the rate constant (min-1) qe and qt are the amount layer (C), respectively. The speed limiting factor is the rate of
of Cr(VI) adsorbed on the surface of seeds at equilibrium (mg adsorption on the surface, and is directly dependent on the
g-1) and time t (min.), respectively. Is the plotted graph of ln intersection of axis y value (C). The calculated values of
(qe-qt) against time, and k1 and q values were determined by intraparticle diffusion are shown in Table 7, where it can be
the slope of the straight line and the values of the y-axis seen that Kf was 0.230.
intercepts, according to the graph shown in Figure 5.
According to the kinetic model pseudo-second-order, 4. CONCLUSION
the occupation rate of adsorption sites is proportional to the Natural organic materials of low cost have been used
square numbers of unoccupied sites [54]. It is expressed by the with alternative adsorbents for the removal of metals from
following equation 8: 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
where k2 (g mg-1 min-1) is the rate constant was determined by potassium. The adsorption of Cr(VI) using NS was
graphic t/qt vs.time (Figure 6). The constants of the pseudo- investigated by changing many parameters during the
first-order and pseudo-second-order, the calculated q values experiment. The initial Cr(VI) amount in the solution phase
and the corresponding values of the regression coefficients are and the pH value of bulk solution influenced the adsorption
shown in Table 7. quantity. The optimum pH for the removal of Cr(VI) by NS
The value of the distribution coefficient (R2) for the was 1.0 at the equilibrium conditions. The maximum uptake
kinetics models of removing of Cr(VI) showed the better of Cr(VI) percentages was obtained as 100% when metal
adjusted to the kinetics of pseudo-second order, as can see the concentration was 10 mg L-1. The adsorption value of
difference between the distribution coefficient of the two chromium was related to contact time and attained to the
models, in which this value was 0.991 for the kinetic pseudo- equilibrium at 30 min for Cr(TOTAL). Data isotherm of Cr(VI)
second order. The estimated value of q e agreed with the adsorption on NS was modelled by Langmuir adsorption
experimental values (3.08 mg g-1), indicating that the rate- model and NS has maximum adsorption capacity of 7.94 mg
limiting step is the chemical adsorption of the ions Cr (VI) and g-1 of Cr(VI) from the aqueous solution. When amount of
NS. However, both kinetic models do not explain the exact adsorbent increased in the solution phase, the retention of
mechanism of adsorption which occurs in the biosorption Cr(VI) increased in the solid phase. The pseudo-second-order
process. However, it can be explained by intraparticle kinetic of the adsorption process was validated with
diffusion model which describes the mechanism of diffusion experimental data. The results indicate that noni seeds was
on the surface of the biosorbent [55] and is given by the shown to be a promising adsorbent for the removal of Cr(VI)
following equation 9 - 10: ions from aqueous solution.
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Table I
Chemical and physical characterization (BET, surface groups and elements) in NS
Pore volume 0.026 cm3 g−1
Pore diameter 93.77 Å
Surface area (BET) 11.13 m2 g−1
Organic material 98.14 (wt %)
Surface groups µmol 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 ν C-OH of phenolics compounds
1643 ν 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 νC-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).
8
6
q (mg g )
-1
4
2
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
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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