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ABSTRACT
Adsorption interactions of radium (Ra) ions onto coir pith (CP) under the presence of humic acid (HA)
in the aqueous solution were investigated using X-ray diffraction (XRD), Fourier Transform Infrared
Spectrophotometer (FTIR) and Scanning Electron Microscopy (SEM) techniques. XRD, IR and SEM
characterization of the CP has revealed differences in the native CP and Ra ions loaded CP under the
presence of HA in the aqueous solution. The X-Ray patterns showed that crystalline structure of the
loaded CP exhibited a decrease in crystalline structure at around 49- 51 compared with unloaded CP.
Characterization by IR revealed that participation of some surface functional groups during the Ra
adsorption. SEM images for the morphological studies showed that there were slightly changes of the
CP surfaces after the adsorption process.
Keywords: Coir pith; radium, humic acid; adsorption; XRD; FTIR; SEM
PACS:
INTRODUCTION
A number of researchers have investigated the use of
agricultural waste material as an adsorbent for the
removal of pollutants in wastewater (Chamorthy et al.,
2001; Basso et al., 2002; Villaescusa et al., 2004; Shibi &
Anirudhan, 2006). The agricultural waste materials have
been found to have good adsorption capacity due to
inherent compound associated with cellulose such as
lignin, tannin and pectin, which contains polyphenolic
and aliphatic hydroxyl and carboxylic groups (Anirudhan
et al., 2008). There are several mechanisms which involve
in the adsorption process by the adsorbent namely Van
der Waals forces, steric interaction, hydrogen bonds,
hydrophobicity and polarity. Hence, the physical and
chemical properties of the adsorbent are very important in
controlling the adsorption process. Burg et al. (2000)
reported that the selectivity and maximal quantity of
pollutant adsorbed are controlled by the chemical
functions at the solid sorbent surface and the solid
specific area. Thus, it is very important to characterize the
adsorbent before and after the adsorption process because
it can help to clarify the potential mechanism involve in
adsorption and provide the physical and chemical
evidence about the success of adsorption.
In this study, coir pith is presented as one biosorbent
alternative for the removal of radium from aqueous
solution. Coir pith (CP) is an indigenously available
agricultural solid waste, which is generated in the process
of coir fiber from coconut husk. Raw coir pith consists of
Table 1 FTIR spectrum of fundamental peaks of HA, native CP (before) and after Ra adsorption (CPHARa) (cm-1)
Compound
O-H
C-H
C=O
C=C
O-CH3
C-OH
HA
CP (native)
3362.8
3341.5
2920.3
2929.1
1705.7
1734.0*
1610.4
1605.3
1414.9
1450.4
1214.4, 1060.3*
1262.9, 1035.1
CPHARa
3329.9
2900.4
1734.6*
1604.0
1424.9
1262.6, 1032.4
weak
Adsorption Experiments
The adsorption or Ra2+ were studied by adding 40 ml
of 16 Bqml-1 226Ra working solution to 10 ml of 0.2
mgml-1 of HAs solutions in 50 ml centrifuge tubes
containing 1.0g of CP and adjusting the pH to 9. The
centrifuge tubes were sealed with screw caps. The
mixtures was then shaken using a flask shaker machine at
300 oscmin-1 for 24 hours at room temperature. At the end
of the adsorption period, the mixtures were filtered and
the adsorbate loaded CP sample was dried in desiccator
before they were characterized.
Characterization methods
The XRD patterns of the adsorbent were obtained with
a PANalytical PW3040/60 diffractometer with Cu-K xray ( = 1.54060 ). The data were collected at room
temperature in the range of 2 between 5 to 60. The
surface morphology of CP before and after the Ra
adsorption was examined by a scanning electron
microscope (SEM) (model FEI 400). The analysis on the
functional groups of native CP before and after the Ra
adsorption was performed using Fourier transform
infrared spectrophotometer (FTIR) (model Spectrum
2000/L183, USA) in the range 400-4000 cm-1.
FTIR results
The FTIR spectra of the HA, native CP before and CP
after the Ra adsorption are shown in Fig. 2. The FTIR
spectrum for the fundamentals peaks of HA, native CP
before and after the Ra adsorption are shown in Table 1.
The FTIR spectrum of HA reveals the main absorption
bands are at 3362.8 cm-1 (H-bonded OH groups), 2920.3
cm-1 (aliphatic C-H stretching), 1705.6 cm-1 (C=0
stretching of COOH and ketonic C=O), 1610 cm-1
(aromatic C=C and H bonded C=O) and 1250 cm-1 (C-O
stretching and O-H deformation of COOH groups). There
are small bands at 1507.0 cm-1 (aromatic C=C), 1407.8
cm-1 (C-H deformation of CH2), 1365.2 cm-1 (O-H
deformation, CH3 bending, or C-O stretching).The FTIR
spectrum of CP before adsorption reveals a broad peak
around 3334.5 cm-1, which can be attributed to the O-H
groups from cellulose structure (Anirudhan et al., 2007).
The peak observed at 2929.1cm-1 corresponds to C-H
stretching. The spectrums at 1800 - 1000 cm-1 were
CP
CPHARa
HA
Fig. 2 FTIR spectrum of HA, CP (before adsorption) and CPHARa (after adsorption at pH 9)
Fig. 3 SEM micrograph (a) native CP (magnification of 200x), (b) CP after the Ra adsorption under the presence of
HA at pH 9 (magnification of 200x) and (c) the close- up of CP after Ra adsorption (magnification of 1000x)
fingerprint regions (Suksabye et al., 2007). These
peaks are corresponding to the carbonyl stretching groups
(1726.9 cm-1), C=C stretching of aromatic ring vibration
(1605.3 cm-1, 1509.2 cm-1), methoxy groups (O-CH3,
1429 cm-1) from lignin structure of CP (Khan et al.,
2004), O-H deformation of phenolic group (1365.2 cm-1)
and C-OH stretching (1262.9 cm-1, 145.3cm-1, 1035 cm-1).
In the FTIR spectrum of CP after the Ra adsorption under
the presence of HAs (CPHARa), it is clear that an OH
stretching vibrational band shows a frequency shift to
lower wave number (3341.5 to 3329.9 cm-1) after the
adsorption process. The shift to lower wavenumber
indicated that the interaction of -OH groups was greater
after Ra adsorption in the presence of HA in aqueous
solutions. It was also observed that there were a small
shift of wave number for an aromatic C=C and C-OH
groups. The shift of wave numbers might indicated that
there were a chemical interaction between the adsorbent,
HA and Ra ions. The C-H stretching groups are shifted to
lower wavenumber. This is due to the increase in C-H
bond distance, delocalization of electron density and thus
the complexes are having proper hydrogen bonded
complexes (Kolandaivel & Nirmala, 2004).
SEM results
SEM image in Figure 3 (a) shows the morphological
of native CP before Ra adsorption at 200x magnification.
At such magnification, the coir pith particles showed that
the CP surface consists of close thin-walled ribbon shape
cells and porous pith tissue were clearly identifiable.
Figure 4(b) shows the SEM image of CP after the Ra
adsorption (magnification of 200x) under the presence of
HAs in aqueous solution. From the image, it could be
seen that there were slightly changed of the CP surfaces
after the adsorption process. The structure of porous pith
tissue was disrupted and tended to coagulate after Ra
adsorption.
CONCLUSION
The present study clearly shows that the
characterization data have confirmed that there was a
change in morphology and surface chemistry of coir pith
before and after the Ra adsorption. The XRD pattern
revealed that the crystalline structures are disrupted due to
Ra adsorption. The FTIR and SEM characterization of the
REFERENCES