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Removal of Ni(II) from aqueous solution using Moringa oleifera seeds as a

bioadsorbent

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DOI: 10.2166/wst.2012.026 · Source: PubMed

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 1435 © IWA Publishing 2012 Water Science & Technology | 65.8 | 2012

Removal of Ni(II) from aqueous solution using

Moringa oleifera seeds as a bioadsorbent
Thiago L. Marques, Vanessa N. Alves, Luciana M. Coelho
and Nívia M. M. Coelho

ABSTRACT
Thiago L. Marques
Metal contaminants are generally removed from effluents by chemical and physical processes which
Vanessa N. Alves
are often associated with disadvantages such as the use of toxic reagents, generation of toxic waste Nívia M. M. Coelho (corresponding author)
Instituto de Química,
and high costs. Hence, new techniques have been developed, among them the study of natural Universidade Federal de Uberlândia,
Av. João Naves de Ávila 2121,
adsorbents, for instance, the use of Moringa oleifera seeds. The potential of M. oleifera seeds for CEP 38400-902,
Uberlândia, MG,
nickel removal in aqueous systems was investigated. The seeds utilized were obtained from plants
Brazil
grown in Uberlândia/Brazil. After being dried and pulverized, the seeds were treated with 0.1 mol/L E-mail: [email protected]

NaOH. Fourier transform infrared spectroscopy, scanning electron microscopy and Luciana M. Coelho
Departamento de Química,
thermogravimetric analyses were used for the characterization of the material. Using the optimized Universidade Federal de Goiás,
Av. Doutor Lamartine Pinto de Avelar,
methodology (50 mL of 4.0 mg/L Ni(II), pH range of 4.0–6.0, agitation time of 5 min and adsorption 1120 Setor Universitário,
CEP 75704-020,
mass of 2.0 g) more than 90% of Ni(II) could be removed from water samples. The sorption data were
Catalão, GO,
fitted satisfactorily by the Langmuir adsorption model. Evaluation applying the Langmuir equation Brazil

gave the monolayer sorption capacity as 29.6 mg/g. The results indicate that this material could be
employed in the extraction of nickel, considering its ease of use, low cost and environmental viability,
which make it highly attractive for application in developing countries.
Key words | adsorption, Moringa oleifera, nickel

INTRODUCTION

In recent years, the contamination of water bodies by toxic extraction and adsorption, have been reported in the litera-
heavy metals through the discharge of industrial waste- ture (Parab et al. ; Conrad & Hansen ; Sari et al.
waters is a world-wide environmental problem. Heavy a, b; Uluozlu et al. ; Vieira et al. ). Studies
metals such as lead, cadmium and nickel are among the have demonstrated that selectivity and efficiency in the
most common pollutants found in industrial effluents. removal of pollution agents, such as heavy metals from
Even at low concentrations, these metals can be toxic to effluents through an adsorption process, are highly depen-
organisms, including humans. dent on the physical properties and chemical composition
Nickel has several applications including its use in the of the adsorbent (Vieira et al. ).
metallurgical industry. The extensive use of nickel in several Moringa oleifera seeds can be considered as a natural
activities means that a considerable amount finds its way adsorbent material which presents some important charac-
into aquatic environments or biological wastewater treat- teristics in relation to its application in effluent treatment.
ment plants (Yang et al. ). Consequently, there is a The seeds have been used for the treatment of turbid
need to remove this toxic metal from wastewater effluents. water due to their flocculation properties. A flocculation
The US EPA has set specific nickel limits for wastewater protein from the seeds of M. oleifera Lam. was isolated by
effluent, which are 2.0 mg/L for short-term effluent reuse Gassenschmidt et al. () and its molecular mass found
and 0.2 mg/L for long-term effluent reuse (US EPA ). to be around 6.5 kDa and the isoelectric point above 10.
Many studies on the removal of heavy metals from water However, the mechanism of coagulation by polypeptides is
and effluents, including chemical precipitation, solvents still unknown.

doi: 10.2166/wst.2012.026
 1436 T. L. Marques et al. | Removal of Ni(II) from aqueous solution using M. oleifera seeds Water Science & Technology | 65.8 | 2012

The use of M. oleifera seeds as a preconcentrator the unshelled seeds were ground in a commercial blender
material in a flow system for Cd(II) determination in alcohol and then classified through a sieve shaker and separated
fuel is reported in the literature (Alves et al. ). Also, our into two particle sizes (0.5 and 1.0 mm). The seeds were
research group has previously performed studies involving treated with 0.1 mol/L NaOH to remove organic and inor-
the treatment of aqueous solutions containing silver ions ganic matter from the sorbent surface.
and percentage removals of around 98% were achieved The M. oleifera seeds were characterized using several
(Araújo et al. ). techniques. Qualitative analysis of the main functional
In this study, M. oleifera seeds were used as a new low- groups involved in metal adsorption was performed using
cost adsorbent to remove Ni(II) from aqueous solution. The a Fourier transform infrared spectrometer (Perkin-Elmer
operating parameters that affect the adsorption process, FTIR 1605, Rodgau, Germany). The experiment was carried
such as pH, agitation time and adsorbent dosage, were out using KBr discs to prepare the seed samples and the
investigated. spectral range varied from 4,000 to 500 cm
1. Thermal
analysis of the seeds was performed using a thermogravi-
metric analyzer (TA Instruments TGA 2950, New Castle,
EXPERIMENTAL PA, USA). Approximately 10 mg of seeds were heated to
W W
950 C in an oxidizing atmosphere at a rate of 20 C/min.
Instrumentation A JEOL JMT-300 (Tokyo, Japan) scanning electron
microscope was used to examine the morphological charac-
A Varian Model SpectrAA-220 (Melbourne, Victoria, Aus- teristics of the seeds and to evaluate the profile of the
tralia) flame atomic absorption spectrometer, with air- material in terms of retaining metal ions.
acetylene flame, was used for the nickel determination.
A hollow cathode lamp was run under the conditions rec-
ommended by the manufacturer and conventional values Batch adsorption experiments
were used for the wavelength, slit width and burner
height. A Gehaka Model PG1800 pH meter (São Paulo, Removal studies using standard Ni(II) solutions were car-
SP, Brazil) was used to set the pH of the samples and ried out in triplicate. The seeds were shaken with 50 mL
working solutions. Magnetic stirrers (Tecnal TE141, of 4 mg/L Ni(II) for 5 min using a magnetic stirrer and
Piracicaba, SP, Brazil) were used in the batch adsorption then the suspension was filtered using filter paper
experiments. (Whatman no. 42). The metals were quantified before
and after the removal experiments. In order to obtain
the optimum conditions in terms of the percentage of
Reagents and solutions
metal removal the following variables were studied:
adsorbent mass (0.5–2.0 g), extraction time (5–40 min)
All working solutions were prepared with ultra-pure water
and pH (2–12).
obtained from a Milli-Q (Bedford, MA, USA) water purifi-
cation system. Reagents were analytical grade. All
laboratory glassware was previously washed with neutral Metal analysis
detergent, and then kept overnight in 10% (v/v) nitric
acid solution and washed with deionized water. The Final residual nickel concentration after adsorption was
working solutions were prepared through dilution of a directly measured by flame atomic absorption spectropho-
1,000 mg/L stock solution of nickel (Carlo Erba, Milano, tometry (FAAS). To estimate the percentage removal of
Italy) in deionized water. Solutions (Vetec, São Paulo, SP, metal ions from aqueous solution the following equation
Brazil) of 0.1 mol/L HNO3 and 0.1 mol/L NaOH were was used:
used to adjust the pH.
Co
Cf
Preparation for bioadsorbent and adsorbent % Adsorption ¼ × 100 (1)
Co
characterization
where Co is the initial metal concentration (mg/L) and Cf is
The M. oleifera seeds were obtained from trees cultivated in the final residual concentration of metal after the adsorption
the city of Uberlândia (Minas Gerais, Brazil). After drying, time.
 1437 T. L. Marques et al. | Removal of Ni(II) from aqueous solution using M. oleifera seeds Water Science & Technology | 65.8 | 2012

Adsorption isotherm

The experiments were carried out in the temperature range

of 25–28 C, using 0.5 g seeds (500 μm) and 50 mL of a Ni
W

(II) solution at a concentration of 5–100 mg/L. The pH of

the mixture was adjusted to between 4 and 6 using
0.5 mol/L NaOH and the extraction time was 20 min. The
mixture was filtrated and the metal ions were quantified
using FAAS.

Studies on potentially interfering ions

The removal of Ni(II) in the simultaneous presence of Mn

(II), Co(II), Cu(II), Cd(II) and Cr(III) in various proportions,
represented by the interfering ions, was evaluated using
Figure 1 | FT-IR spectrum of Moringa oleifera seeds in natura and treated with NaOH.
unshelled seeds treated with NaOH. Ni(II):interfering ions
ratios were 1:1, 1:2 and 1:4. The experimental conditions
were: particle size of 500 μm, extraction time of 5 min, sor- The spectra for the material in natura and modified with
bent mass of 2.0 g and pH between 4 and 6. NaOH present almost the same profile, with peaks charac-
teristic of lignocellulosic materials. The broad band in the
Application of the proposed method region of 3,750–3,000 cm
1 is associated with stretching of
the O–H and N–H groups present in proteins, fatty acids,
The proposed sorbent was applied to samples obtained from carbohydrates (cellulose and hemicellulose) and lignin
aqueous systems. These samples were collected from the fol- (Gardea-Hernández et al. ). Both have intense peaks
lowing: three different locations along the Pirapitinga creek in the region of 1,745 cm
1, characterized by C5 5O stretch-
which runs through an urban zone in the city of Catalão ing of the acetyl ester and carbonyl groups of
(Goiás, Brazil) and a sample of drinking water treated by a hemicellulose and lignin aldehydes, respectively. The
sanitation company and collected from a residential prop- intense broad band present at 1,654 cm
1 band is associated
erty. In these samples the concentration of Ni(II) was low with water absorbed in the material. The peaks at 1,099,
and therefore, to assess the performance of the adsorbent 1,062 and 1,033 cm
1 are due to the C–O stretching, and
material in real systems, these samples were spiked with a are characteristic bands of cellulose and hemicellulose from
4 mg/L Ni(II) solution. Samples were filtered through filter lignocellulosic materials. The main differences between the
paper and the pH adjusted to within the range of between two spectra are the increase in the bands at around 3,400
4 and 6 using 0.5 mol/L NaOH. 50 mL samples were and 1,745 cm
1 due to an increased amount of hydroxyl
shaken for 5 min with 2.0 g of unshelled seeds treated with groups and lignin content in the material modified with
NaOH and nickel ions were quantified using FAAS before NaOH. The decrease in the peaks at 1,099, 1,062 and
and after the removal experiments. 1,033 cm
1 is due to hydrolysis of some of the cellulose and
hemicellulose present in the material modified with NaOH.
Thermogravimetric analysis was used to characterize
RESULTS AND DISCUSSION the decomposition stages and thermal stability of the
material. With respect to the thermogravimetric exper-
Characterization of the adsorbent material iments, the global mass loss of the seeds in natura and
treated with NaOH, the occurrence of five stages of thermal
The FT-IR technique was used to study the main functional decomposition were observed for both materials as follows:
W W W W
groups present in moringa seeds. This technique allows 30–110 C, 110–220 C, 220–420 C, 420–620 C and 620–
W
some important functional groups which are capable of 900 C. For the material in natura the mass loss of around
W
adsorbing metal ions to be identified. The spectra obtained 9.2% which occurs at between 30 and 110 C is associated
for the material in natura and treated with NaOH are with the loss of humidity. The second event, observed at
W
shown in Figure 1. between 110 and 220 C, represents a stationary stage
 1438 T. L. Marques et al. | Removal of Ni(II) from aqueous solution using M. oleifera seeds Water Science & Technology | 65.8 | 2012

where there is no decomposition of the material. In the The nickel adsorption after different contact periods was
W
temperature range of 220–420 C there was a 60.2% loss in studied keeping all other parameters constant. The
the mass of moringa in natura due to the decomposition amount of nickel ions retained by the adsorbent material
of proteins, hemicellulose, cellulose, fatty acids and lignin, increased for up to 20 min and remained constant
this being the sequence of increasing thermal stability of thereafter. A period of 5 min was chosen due to the good
W
these constituents. In the temperature range of 420–620 C results obtained applying the shortest time studied in the
a mass loss of 27.6% was observed, corresponding to the sorption process.
combustion of residual lignin, as well as the mineralization The effect of pH on the Ni(II) adsorption was studied
of the material. The thermogram obtained for the seeds trea- from pH 2.0–12.0. Optimum values of Qe were obtained at
ted with 0.1 mol/L NaOH showed characteristics similar to pH > 4.0 and above this pH value the percentage removal
W
those described above, but the loss of humidity at 30–110 C remained constant. In adsorption processes the pH is one
was only 6.1%. In the third stage the percentage of mass loss of the most important parameters to be evaluated and the
was higher (63.3%) and was shifted to higher temperatures. ionic states of functional groups can be used to explain the
It was also observed that, in the fourth stage, there was a pH dependence of biosorption. Low pH conditions allow
decrease in the percentage of residual lignin to 24.5%. hydrogen and hydronium ions to compete with metal bind-
This finding demonstrates that the treatment led to ing sites on the biomass, causing poor uptake. Biosorbent
increased thermal stability of the material. materials primarily contain weak acidic and basic functional
Figure 2 shows the scanning electron micrographs of the groups. It follows from the theory of acid–base equilibrium
seeds. It appears that the treatment with NaOH increased that, in the pH range of 2.5–5, the binding of heavy metal
the porosity of the material (Figure 2(b)), making it more cations is determined primarily by the dissociation state of
exposed to the adsorption of metal species. This change in the weak acidic groups. Carboxyl groups (–COOH) are
the morphology of the material also results from the removal important groups for metal uptake by biological materials.
of some superficial structural components such as carbo- At higher solution pH values precipitation occurs, leading
hydrates, proteins and lignin. to a reduced sorption capacity. Therefore, the pH range of
4.0–6.0 was chosen for further studies. According to
Determination of optimum parameters and adsorption Srivastava et al. (), in this pH range there is only the
studies form of Ni2þ. The pHpcz (pH of point of zero charge) for
M. oleifera seeds is between 6.0 and 7.0 (Alves et al. ).
The influence of the adsorbent dosage on nickel sorption According to Abollino et al. (), the affinity between
was studied by varying the amount of adsorbent from 0.5 metal ions depends not only on pH but also on presence of
to 2.0 g. The percentage adsorption of nickel increased ligands in solution. Thus, in our study, the pH was not buf-
with an increase in the adsorbent mass for up to 2.0 g. fered in order to reduce interferences in adsorptive process.
This trend is to be expected because as the adsorbent dose
increases the number of adsorbent particles also increases Adsorption isotherm
and there is greater availability of sites for adsorption.
Thus, the mass of 2.0 g of bioadsorbent was chosen for An important physicochemical aspect in terms of the
further studies. evaluation of sorption process is the sorption equilibrium.

Figure 2 | Scanning electron micrograph of Moringa oleifera. In natura (a) and treated with NaOH (b).
 1439 T. L. Marques et al. | Removal of Ni(II) from aqueous solution using M. oleifera seeds Water Science & Technology | 65.8 | 2012

Figure 3(a) shows the sorption isotherm for Ni(II) adsorp- solution also containing potentially interfering ions. The
tion onto unshelled seeds. removal percentage was calculated based on the analytical
The experimental data fitted to Langmuir linear signals obtained before and after the removal procedure. A
equation expressed as the following equation: species is considered as interferent when the difference
between the values is more than 10% (Araújo et al. ).
Ce Ce 1 In the present method, there are interferences of Mn(II),
¼ þ
Qe Qm KL Qm Co(II), Cu(II), Cd(II) and Cr(III) for ratio greater than 1:4.
The values obtained verified the excellent potential for the
where Ce is equilibrium concentration of the metal (mg/L) removal of Ni(II) ions using M. oleifera seeds. The method-
and Qe is the amount of the metal adsorbed (mg) per unit ology is simple, low cost and can therefore be used in
of adsorbent (g). Qm and KL are Langmuir constants related remediation systems.
to adsorption capacity (mg/g) and the energy of adsorption
(L/g), respectively. Comparison of the material used in the present study
The isotherm curve obtained indicates favourable with other adsorbents
adsorption and the formation of a monolayer. Therefore,
the extent of sorption was appropriate for the application The results of this study showed that M. oleifera seeds
of the Langmuir model. The Langmuir equation assumes demonstrate good removal capacities for Ni(II) (29.6 mg/g)
that adsorption is limited to the monolayer and a maximum when compared with results reported for other adsorbents
adsorption indicates saturation of this monolayer. The (15.95 mg/g for coir pith, 7.9 mg/g for Cladonia furcata
experimental results obtained were plotted (correlation coef- and 1.12 mg/g for bagasse fly ash). A low cost, easy purchase
ficient 0.99127) using the Langmuir isotherm linear and the satisfactory experimental results indicated that seed
equation from 5 to 100 mg/L for metal ions (Figure 3(b)). is an effective adsorbent for Ni(II) removal from aqueous
The plot of Ce/Qe versus Ce gives a straight line of slope solution and has the advantage of the fact that it does not
1/Qmax and intercept 1/(b.Qmax). The magnitude of Langmuir need to be previously subjected to chemical or thermal
Qmax showed an adsorption capacity of 29.6 mg of Ni(II) treatment.
per gram of M. oleifera seeds.
Application
Studies on interfering ions in Ni removal
The proposed method was applied in the treatment of water
The influence of Mn(II), Co(II), Cu(II), Cd(II) and Cr(III) in samples. In these samples the concentration of the Ni(II)
various proportions was verified by comparing the percen- ions was low and thus they were spiked with Ni(II) at
tage removal from a solution containing only Ni(II) and a a concentration of 4.0 mg/L. The pH of samples was

Figure 3 | Adsorption isotherm for Ni(II) by Moringa oleifera seeds (a) and Langmuir linearized isotherm (b).
 1440 T. L. Marques et al. | Removal of Ni(II) from aqueous solution using M. oleifera seeds Water Science & Technology | 65.8 | 2012

Table 1 | Use of Moringa oleifera seeds treated with NaOH in Ni(II) removal in aqueous
samples
REFERENCES

Sample Ni(II) added (mg/L) Ni(II) found (mg/L) Removal (%) Abollino, O., Aceto, M., Malandrino, M., Sarzanini, C. &
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A 0 0.36 108 (±10) montmorillonite. Effect of pH and organic substances. Water
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4.0 4.35 Araújo, C. S. T., Melo, E. I., Alves, V. N. & Coelho, N. M. M. 
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ACKNOWLEDGEMENTS
2980.
US EPA  Guidelines for Water Reuse. EPA/625/R-04/108, US
The authors are grateful for financial support of the follow- Agency for Inter. Development, Washington, DC, USA.
ing governmental agencies: Conselho Nacional de Vieira, M. G. A., Neto, A. F. A., Gimenes, M. L. & Silva, M. G. C.
Desenvolvimento Científico e Tecnológico (CNPq), Coorde-  Removal of nickel on Bofe bentonite calcined clay in
porous bed. J. Hazard. Mater. 176, 109–118.
nação de Aperfeiçoamento de Pessoal de Nível Superior
Yang, Q. Z., Qi, G. J., Low, H. C. & Song, B.  Sustainable
(CAPES), Fundação de Amparo à Pesquisa do Estado de recovery of nickel from spent hydrogenation catalyst:
Minas Gerais (FAPEMIG) and Fundação de Amparo á Pes- economics, emissions and wastes assessment. J. Clean.
quisa do Estado de Goiás (FAPEG). Product. 19, 365–375.

First received 29 September 2011; accepted in revised form 2 December 2011

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