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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
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 0<RL<1 to Cr(III) and the determination of the metal reduction is an
the sorption process is favourable. important parameter, given that not all the Cr(VI) is removed
From the experimental results the Langmuir model by adsorption [47].
isotherm fits quite well with the experimental data According to results shown in Figure 4, was observed
(distribution coefficient, R2 = 0.95) at room temperature (25 that the removing kinetics of Cr(VI) and Cr (TOTAL) is fast
C). The removal of Cr(VI) is favorable because of value R L during the 10 min, because the process mainly occurs in the
(0<RL<1). The adsorption involves the formation of a outer surface of NS. Then a slow phase (10 - 30 min) occurs in
monolayer Cr(VI) in NS surface. The values given in Table 5 inner surface of NS. In these instants, the Cr(VI) concentration
indicate that the Langmuir model was suitable for balance and decreases considerably when compared to the Cr (TOTAL). This
isotherm fits for the removal of Cr(VI). Maximum Cr (VI) process can be explained due of reducing the Cr(VI) to Cr(III)
adsorption capacity was 7.94 mg g-1 for NS (Table 5). by surface groups (phenols and carbonyls). After 30 min., a
constancy in the concentration of Cr(TOTAL) determines that the
Freundlich isotherm adsorption equilibrium was reached but the reduction is still.
The linear form of the Freundlich is expressed by the The results indicates that initially prevailed removal
equation 5 and the model proposes an adsorption multilayer by adsorption of Cr(VI) and later by metal reduction (Cr(VI)
and the isotherm adsorption equation can be written as [44]: 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
where Kf is a constant related to the Freundlich adsorption tannins and phenolic compounds, substances that are present
capacity (L mg-1) and n represents the heterogeneous factor in the NS because of their chemical characterization of surface
related to the intensity of adsorption of the Cr(VI) and NS, groups [50], and also because the substance which is the
where 1/n=0 reversible, 1/n<0 unfavorable, 1/n>0 favorable material such as americanin A [51] which is a phenol having a
sorption. good oxidation potential [52], may further reduce the Cr (VI)
to Cr (III). The percentage removal of Cr (TOTAL) in peanut
Temkin isotherm hulls, wood and orange peel sheet similar to the percentage
The Temkin isotherm model contains a factor that found in this study (approximately 40%) [47].
takes into account specifically only the adsorbent-adsorbate
interactions, by neglecting the low and high concentration 3.3.1 Adsorption kinetics
values, and it is assumed that the decrease in sorption heat is
linear rather than logarithmic, implied in the Freundlich Kinetic studies are important in determining the
adsorption rate and describe the solute gain rate, which affects
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
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
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).
50
Cr(VI)
Cr(TOTAL)
-1
Cr(III)
30
20
10
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)
80
70
60
50
40
t/qt 30
20
10
0
0 50 100 150 200 250
Time (min)
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