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International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019
Available at www.ijsred.com
ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 538
STUDY OF CONTACT TIME ON EFFECTIVENESS OF NATURAL
ADSORBENTS TO ADSORB CRYSTAL VIOLET DYE
Sudevi Basu*, Tanushree Deb and Vanitha Nagliekar
Department of Biotechnology, Sir M Visvesvaraya Institute of Technology, Bengaluru – 562157, Karnataka, India
Abstract:
Synthetic dyes are used for colouring in textile, leather and manufacturing industries and these
are water soluble and produce very bright colours in water. When it is discharged without
treatment, it leads to pollution. This research gives an insight into the adsorption studies with a
focus on time of contact on the efficiency of decolourizing Crystal Violet dye with natural
adsorbents (Citrullus lanatus Peel, Citrullus lanatus Rind and Citrus limetta Peel). This study
reveals that Citrullus lanatus Rind can effectively decolourize 52.2% Crystal Violet dye at
concentration of 50 mg/L with lower contact time of 60 min and at 120 min, 67.7% dye removal
is achieved. At increased initial dye concentration of 75 mg/L and 100 mg/L, Citrullus lanatus
Peel is effective in decolourizing Crystal Violet dye at lower contact time of 60 min and
percentage dye removal is 67.4% and 65% respectively. At high initial dye concentration of 125
mg/L, high contact time of 120 min with Citrullus lanatus Peel is required to remove 58.8%
Crystal Violet Dye. As compared with these two adsorbents, Citrus limetta Peel is not very
effective in adsorbing Crystal Violet Dye.
Keywords: Citrullus lanatus Peel, Citrullus lanatus Rind and Citrus limetta Peel, Adsorbents
Introduction
The synthetic dyes are chemical compounds
which create havoc in the environment if
untreated and let into water bodies because
these are water soluble, retain in the
environment, are difficult to degrade due to
their complex aromatic structures, pollute
the water bodies, affect aquatic life, enter
into food webs and have carcinogenic and
mutagenic effects (Vinoth et al., 2010;
Abbas et al., 2011; Karthik et al., 2012).
Most of these are azo dyes and the presence
of one or several azo (–N=N–) groups
associated with substituted aromatic
structures impart bright colour (Vinoth et
al., 2010). Amongst various physical
techniques to decolourize dyes, adsorption
has gained prominence due to its
effectiveness and efficiency for the removal
of colour from the wastewater (Sharma et
al., 2005; Karthik et al., 2012). However,
the traditional adsorption technique
employing solid activated carbon is costly
and the modern focus is on the use of natural
adsorbents. This research is focused on the
effect of contact time with waste natural
adsorbents like Watermelon (Citrullus
lanatus) Peel and Rind and Musambi (Citrus
limetta) Peel in decolourizing the synthetic
dye, Crystal Violet.
RESEARCH ARTICLE OPEN ACCESS
International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019
Available at www.ijsred.com
ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 539
2. Materials and Methodology
2.1 Preparation of Adsorbent
Citrullus lanatus Peel and Citrus limetta
Peel are collected from Sir MVIT canteen
and are thoroughly washed with distilled
water. The Citrullus lanatus Rind is
carefully removed from the Peel and all
these are dried under the sun until these have
become crisp so as to crush these separately
into powder form in mixer and are passed
through a 0.246 mm sieve to obtain uniform
particle size of adsorbents. The size of the
sieve is chosen according to the study by
Karim et al., 2015. The adsorbents are then
stored in air tight containers.
2.2 Preparation of Adsorbate
A stock solution of Crystal Violet dye is
prepared by dissolving 0.5 g of dye in 1 L
distilled water and stored in volumetric
flask.
2.3 Batch Studies on Contact Time
Aliquots of the dyes are prepared to obtain
solutions with concentrations 50 – 125
mg/L. The volume is made to 100 mL.
These dyes are taken in 250 mL conical
flasks and 0.5g of three adsorbents are
weighed separately and added to each
conical flask. The solutions are agitated at a
speed of 240 wrist action per minute using
Secor India Griffin Flask Shaker for 60
minutes, 90 minutes and 120 minutes at a
constant room temperature of 330
C. After
the stipulated time, the adsorbate is filtered
out using ordinary filter paper from each of
the conical flasks in order to get a clear
solution. Optical Density is measured at 650
nm using Systronics Spectrophotometer
(Model-106). The process is repeated again
for all the adsorbents.
The percentage removal of adsorbate
adsorbed on the adsorbent is calculated as
( )
100*Re%
0
0
C
CC
movalDye
f−
= ---------(1)
Where 0C = Initial Concentration of Dye
(mg/L)
fC = Final Concentration of Dye
after Adsorption (mg/L)
3. Results and Discussion
Figure 1 shows that with 0.5 gm and 0.246
mm Citrus limetta Peel adsorbent, the
percentage dye removal for Crystal Violet
dye at initial concentration of 50 mg/L and
is found to be 20.5%, 23% and 24.5% at
contact time of 60 min, 90 min and 120 min
respectively. Substantial increase in
percentage dye removal has been seen at
initial concentration of dye at 75 mg/L and it
is 25.5%, 36.4% and 37.3% at contact time
of 60 min, 90 min and 120 min respectively.
This can be due to the availability of more
time for the dye to form an attraction
complex with the adsorbents. This is similar
to the findings of researchers Abbas et al.,
2011 and Karthik et al., 2012, Basu et al.,
2017. However, the percentage dye removal
is almost constant even with increase in
contact time at higher initial dye
concentration of 100 mg/L and 125 mg/L at
24.5 % and 29% respectively. This may be
due to the fact that equilibrium is reached
and also the binding of functional groups on
the surface of adsorbent by dye may be
weak. This is similar to the work by Said et
al., 2014.
International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019
Available at www.ijsred.com
ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 540
Figure 1 Percentage Dye Removal of Crystal
Violet Dye with Citrus limetta Peel
Adsorbent Dose of 0.5 gm and size 0.246
mm
Figure 2 shows the percentage dye removal
of Crystal Violet dye with Citrullus lanatus
Rind adsorbent dose of 0.5 gm and size
0.246 mm. At initial concentration of 50
mg/L, the percentage dye removal at 60 min
is 52.5% and increases to 67.7% at 120 min.
Citrullus lanatus Rind shows a dye removal
percentage of 48.2% at 60 min with initial
dye concentration of 75 mg/L which
decreases at 90 min and increases and
remains constant at 48.6% at 120 min. This
may be because equilibrium might be
reached at 60 min itself. With increase in
initial concentration to 100 mg/L, the dye
removal percentage is almost constant and
varies from 27% to 29.1% even with
increase in contact time from 60 min to 120
min. At 125 mg/L the dye removal
percentage is very low and is 13% at 60 min
contact time and 12.4% at 120 min contact
time.
Figure 2 Percentage Dye Removal of Crystal
Violet Dye with Citrullus lanatus Rind
Adsorbent Dose of 0.5 gm and size 0.246
mm
Figure 3 shows the changes in percentage of
dye removal from initial to final
concentration of dyes with Citrullus lanatus
Peel adsorbent dose of 0.5 gm and size
0.246 mm with varying contact time. At
initial concentration of 50 mg/L, there has
been a sharp decline in percentage dye
removal from 49.1% at 60 min to 9.9% at
120 min. Similarly a decline is observed
from 60 min to 120 min at initial dye
concentration of 75 mg/L and 100 mg/L but
the rate of decline is low from 67.4% to
56.6% and 65% to 52.5% respectively. This
may be due to the dyes remaining in solution
as binding of functional groups on surface of
adsorbent is weak, similar to study by Said
et al., 2014. However, at initial dye
concentration of 125 mg/L, a slight increase
in percentage dye removal is observed with
increase in contact time from 56.6% at 60
min to 58.8% at 120 min. This is because
the adsorbed dye molecules tend to increase
adsorption of other molecules. This is
similar to the work done by Vinoth et al.,
2010. Also more time becomes available for
the dye to make an attraction complex with
0
10
20
30
40
50 75 100 125
%Dyeremoval
Initial Dye Concentration (mg/L)
60 Min
90 Min
120 Min
0
20
40
60
80
50 75 100 125
%Dyeremoval
Initial Dye Concentration (mg/L)
60 Min
90 Min
120 Min
International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019
Available at www.ijsred.com
ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 541
the adsorbents. This is similar to work
carried out by Abbas et al., 2011 and
Karthik et al., 2012, Basu et al., 2017.
Figure 3 Percentage Dye Removal of Crystal
Violet Dye with Citrullus lanatus Peel
Adsorbent Dose of 0.5 gm and size 0.246
mm
4. Conclusion
This study reveals that Citrullus lanatus
Rind is effective in decolourizing 52.2%
Crystal Violet dye at concentration of 50
mg/L with lower contact time of 60 min and
at 120 min, 67.7% dye removal is achieved.
At increased initial dye concentration of 75
mg/L and 100 mg/L, Citrullus lanatus Peel
is effective in decolourizing Crystal Violet
dye at lower contact time of 60 min and
percentage dye removal is 67.4% and 65%
respectively. At high initial dye
concentration of 125 mg/L, high contact
time of 120 min with Citrullus lanatus Peel
is required to remove 58.8% Crystal Violet
Dye. As compared with these two
adsorbents, Citrus limetta Peel is not very
effective in adsorbing Crystal Violet Dye
Acknowledgement
The authors acknowledge the facilities and
resources provided by the Department of
Biotechnology, Sir M. Visvesvaraya
Institute of Technology, Bengaluru, for
carrying out this research work.
References
1. Abbas A., Murtaza S. and Munir M.,
(2011), “Removal of Congo Red
from Aqueous Solutions with
RaphanussativusPeels and Activated
Carbon: A Comparative Study”,
American-Eurasian Journal of
Agricultural and Environmental
Science, Vol. 10, No. 5, pp 802-809.
2. Basu S, Rai D, Harish V,
Shivaraman B. and Tanveer
Madihalli., (2017).,“Effect of
Important Parameters on Adsorption
Efficiency of Methylene Blue Dye”,
International Journal for Science and
Advance Research in Technology ,
Vol. 3, Issue 12, pp 258 – 261.
3. Basu S., Juhi, Kavya H, Dash R and
Sumi, (2017).,“Comparison of
Decolourizing Efficiency of Waste
Pisum Sativum Pod Adsorbent on
Single and Mixture of Synthetic
Dyes”, International Journal for
Scientific Research & Development,
Vol. 5, Issue 06, pp 845 – 851.
4. Karim A S. K., Rabuyah NI., Asli M
A. and Ismail S H., (2015).,
“Removal of Crystal Violet Dye
Using Sugarcane Fibre”,
Transactions on Science and
Technology, Vol. 2, No. 2, pp. 11 –
15.
5. Karthik J. P. M., Swathik H, Baskar
U. S. and Sivamani S., (2012),
“Removal of Direct Red Dye Using
0
10
20
30
40
50
60
70
80
50 75 100 125
%Dyeremoval
Initial Dye Concentration (mg/L)
60 Min
90 Min
120 Min
International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019
Available at www.ijsred.com
ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 542
Neem Leaf Litter”, Helix, Vol. 1,
No. 2, pp 129 – 133.
6. Said A., Hakim M. S.and Rohyami
Y., (2014), “The Effect of Contact
Time and pH on Methylene Blue
removal by Volcanic Ash”,
International Conference on
Chemical, Biological and
Environmental Sciences
(ICCBES’14), May 12 – 13, Kuala
Lumpur (Malaysia)
7. Sharma A. and Bhattacharya K. G.,
(2005), “Utilization of a Biosorbent
based on Azadirachtaindica(Neem)
Leaves for Removal of Water-
Soluble Dyes”, Indian Journal of
Chemical Technology, Vol. 12, pp.
285 – 295.
8. Vinoth M., Lim H. Y., Xavier R.,
Marimuthu K., Sreeramanan S.,
Rosemal M. H. M. H. and Kathiresan
S., (2010), “Removal of Methyl
Orange from Solutions Using Yam
Leaf Fibres”, International Journal of
Chem Tech Research, Vol. 2, No. 4,
pp 1892 – 1900.

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IJSRED-V2I3P64

  • 1. International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019 Available at www.ijsred.com ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 538 STUDY OF CONTACT TIME ON EFFECTIVENESS OF NATURAL ADSORBENTS TO ADSORB CRYSTAL VIOLET DYE Sudevi Basu*, Tanushree Deb and Vanitha Nagliekar Department of Biotechnology, Sir M Visvesvaraya Institute of Technology, Bengaluru – 562157, Karnataka, India Abstract: Synthetic dyes are used for colouring in textile, leather and manufacturing industries and these are water soluble and produce very bright colours in water. When it is discharged without treatment, it leads to pollution. This research gives an insight into the adsorption studies with a focus on time of contact on the efficiency of decolourizing Crystal Violet dye with natural adsorbents (Citrullus lanatus Peel, Citrullus lanatus Rind and Citrus limetta Peel). This study reveals that Citrullus lanatus Rind can effectively decolourize 52.2% Crystal Violet dye at concentration of 50 mg/L with lower contact time of 60 min and at 120 min, 67.7% dye removal is achieved. At increased initial dye concentration of 75 mg/L and 100 mg/L, Citrullus lanatus Peel is effective in decolourizing Crystal Violet dye at lower contact time of 60 min and percentage dye removal is 67.4% and 65% respectively. At high initial dye concentration of 125 mg/L, high contact time of 120 min with Citrullus lanatus Peel is required to remove 58.8% Crystal Violet Dye. As compared with these two adsorbents, Citrus limetta Peel is not very effective in adsorbing Crystal Violet Dye. Keywords: Citrullus lanatus Peel, Citrullus lanatus Rind and Citrus limetta Peel, Adsorbents Introduction The synthetic dyes are chemical compounds which create havoc in the environment if untreated and let into water bodies because these are water soluble, retain in the environment, are difficult to degrade due to their complex aromatic structures, pollute the water bodies, affect aquatic life, enter into food webs and have carcinogenic and mutagenic effects (Vinoth et al., 2010; Abbas et al., 2011; Karthik et al., 2012). Most of these are azo dyes and the presence of one or several azo (–N=N–) groups associated with substituted aromatic structures impart bright colour (Vinoth et al., 2010). Amongst various physical techniques to decolourize dyes, adsorption has gained prominence due to its effectiveness and efficiency for the removal of colour from the wastewater (Sharma et al., 2005; Karthik et al., 2012). However, the traditional adsorption technique employing solid activated carbon is costly and the modern focus is on the use of natural adsorbents. This research is focused on the effect of contact time with waste natural adsorbents like Watermelon (Citrullus lanatus) Peel and Rind and Musambi (Citrus limetta) Peel in decolourizing the synthetic dye, Crystal Violet. RESEARCH ARTICLE OPEN ACCESS
  • 2. International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019 Available at www.ijsred.com ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 539 2. Materials and Methodology 2.1 Preparation of Adsorbent Citrullus lanatus Peel and Citrus limetta Peel are collected from Sir MVIT canteen and are thoroughly washed with distilled water. The Citrullus lanatus Rind is carefully removed from the Peel and all these are dried under the sun until these have become crisp so as to crush these separately into powder form in mixer and are passed through a 0.246 mm sieve to obtain uniform particle size of adsorbents. The size of the sieve is chosen according to the study by Karim et al., 2015. The adsorbents are then stored in air tight containers. 2.2 Preparation of Adsorbate A stock solution of Crystal Violet dye is prepared by dissolving 0.5 g of dye in 1 L distilled water and stored in volumetric flask. 2.3 Batch Studies on Contact Time Aliquots of the dyes are prepared to obtain solutions with concentrations 50 – 125 mg/L. The volume is made to 100 mL. These dyes are taken in 250 mL conical flasks and 0.5g of three adsorbents are weighed separately and added to each conical flask. The solutions are agitated at a speed of 240 wrist action per minute using Secor India Griffin Flask Shaker for 60 minutes, 90 minutes and 120 minutes at a constant room temperature of 330 C. After the stipulated time, the adsorbate is filtered out using ordinary filter paper from each of the conical flasks in order to get a clear solution. Optical Density is measured at 650 nm using Systronics Spectrophotometer (Model-106). The process is repeated again for all the adsorbents. The percentage removal of adsorbate adsorbed on the adsorbent is calculated as ( ) 100*Re% 0 0 C CC movalDye f− = ---------(1) Where 0C = Initial Concentration of Dye (mg/L) fC = Final Concentration of Dye after Adsorption (mg/L) 3. Results and Discussion Figure 1 shows that with 0.5 gm and 0.246 mm Citrus limetta Peel adsorbent, the percentage dye removal for Crystal Violet dye at initial concentration of 50 mg/L and is found to be 20.5%, 23% and 24.5% at contact time of 60 min, 90 min and 120 min respectively. Substantial increase in percentage dye removal has been seen at initial concentration of dye at 75 mg/L and it is 25.5%, 36.4% and 37.3% at contact time of 60 min, 90 min and 120 min respectively. This can be due to the availability of more time for the dye to form an attraction complex with the adsorbents. This is similar to the findings of researchers Abbas et al., 2011 and Karthik et al., 2012, Basu et al., 2017. However, the percentage dye removal is almost constant even with increase in contact time at higher initial dye concentration of 100 mg/L and 125 mg/L at 24.5 % and 29% respectively. This may be due to the fact that equilibrium is reached and also the binding of functional groups on the surface of adsorbent by dye may be weak. This is similar to the work by Said et al., 2014.
  • 3. International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019 Available at www.ijsred.com ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 540 Figure 1 Percentage Dye Removal of Crystal Violet Dye with Citrus limetta Peel Adsorbent Dose of 0.5 gm and size 0.246 mm Figure 2 shows the percentage dye removal of Crystal Violet dye with Citrullus lanatus Rind adsorbent dose of 0.5 gm and size 0.246 mm. At initial concentration of 50 mg/L, the percentage dye removal at 60 min is 52.5% and increases to 67.7% at 120 min. Citrullus lanatus Rind shows a dye removal percentage of 48.2% at 60 min with initial dye concentration of 75 mg/L which decreases at 90 min and increases and remains constant at 48.6% at 120 min. This may be because equilibrium might be reached at 60 min itself. With increase in initial concentration to 100 mg/L, the dye removal percentage is almost constant and varies from 27% to 29.1% even with increase in contact time from 60 min to 120 min. At 125 mg/L the dye removal percentage is very low and is 13% at 60 min contact time and 12.4% at 120 min contact time. Figure 2 Percentage Dye Removal of Crystal Violet Dye with Citrullus lanatus Rind Adsorbent Dose of 0.5 gm and size 0.246 mm Figure 3 shows the changes in percentage of dye removal from initial to final concentration of dyes with Citrullus lanatus Peel adsorbent dose of 0.5 gm and size 0.246 mm with varying contact time. At initial concentration of 50 mg/L, there has been a sharp decline in percentage dye removal from 49.1% at 60 min to 9.9% at 120 min. Similarly a decline is observed from 60 min to 120 min at initial dye concentration of 75 mg/L and 100 mg/L but the rate of decline is low from 67.4% to 56.6% and 65% to 52.5% respectively. This may be due to the dyes remaining in solution as binding of functional groups on surface of adsorbent is weak, similar to study by Said et al., 2014. However, at initial dye concentration of 125 mg/L, a slight increase in percentage dye removal is observed with increase in contact time from 56.6% at 60 min to 58.8% at 120 min. This is because the adsorbed dye molecules tend to increase adsorption of other molecules. This is similar to the work done by Vinoth et al., 2010. Also more time becomes available for the dye to make an attraction complex with 0 10 20 30 40 50 75 100 125 %Dyeremoval Initial Dye Concentration (mg/L) 60 Min 90 Min 120 Min 0 20 40 60 80 50 75 100 125 %Dyeremoval Initial Dye Concentration (mg/L) 60 Min 90 Min 120 Min
  • 4. International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019 Available at www.ijsred.com ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 541 the adsorbents. This is similar to work carried out by Abbas et al., 2011 and Karthik et al., 2012, Basu et al., 2017. Figure 3 Percentage Dye Removal of Crystal Violet Dye with Citrullus lanatus Peel Adsorbent Dose of 0.5 gm and size 0.246 mm 4. Conclusion This study reveals that Citrullus lanatus Rind is effective in decolourizing 52.2% Crystal Violet dye at concentration of 50 mg/L with lower contact time of 60 min and at 120 min, 67.7% dye removal is achieved. At increased initial dye concentration of 75 mg/L and 100 mg/L, Citrullus lanatus Peel is effective in decolourizing Crystal Violet dye at lower contact time of 60 min and percentage dye removal is 67.4% and 65% respectively. At high initial dye concentration of 125 mg/L, high contact time of 120 min with Citrullus lanatus Peel is required to remove 58.8% Crystal Violet Dye. As compared with these two adsorbents, Citrus limetta Peel is not very effective in adsorbing Crystal Violet Dye Acknowledgement The authors acknowledge the facilities and resources provided by the Department of Biotechnology, Sir M. Visvesvaraya Institute of Technology, Bengaluru, for carrying out this research work. References 1. Abbas A., Murtaza S. and Munir M., (2011), “Removal of Congo Red from Aqueous Solutions with RaphanussativusPeels and Activated Carbon: A Comparative Study”, American-Eurasian Journal of Agricultural and Environmental Science, Vol. 10, No. 5, pp 802-809. 2. Basu S, Rai D, Harish V, Shivaraman B. and Tanveer Madihalli., (2017).,“Effect of Important Parameters on Adsorption Efficiency of Methylene Blue Dye”, International Journal for Science and Advance Research in Technology , Vol. 3, Issue 12, pp 258 – 261. 3. Basu S., Juhi, Kavya H, Dash R and Sumi, (2017).,“Comparison of Decolourizing Efficiency of Waste Pisum Sativum Pod Adsorbent on Single and Mixture of Synthetic Dyes”, International Journal for Scientific Research & Development, Vol. 5, Issue 06, pp 845 – 851. 4. Karim A S. K., Rabuyah NI., Asli M A. and Ismail S H., (2015)., “Removal of Crystal Violet Dye Using Sugarcane Fibre”, Transactions on Science and Technology, Vol. 2, No. 2, pp. 11 – 15. 5. Karthik J. P. M., Swathik H, Baskar U. S. and Sivamani S., (2012), “Removal of Direct Red Dye Using 0 10 20 30 40 50 60 70 80 50 75 100 125 %Dyeremoval Initial Dye Concentration (mg/L) 60 Min 90 Min 120 Min
  • 5. International Journal of Scientific Research and Engineering Development-– Volume 2 Issue 3, May 2019 Available at www.ijsred.com ISSN : 2581-7175 ©IJSRED:All Rights are Reserved Page 542 Neem Leaf Litter”, Helix, Vol. 1, No. 2, pp 129 – 133. 6. Said A., Hakim M. S.and Rohyami Y., (2014), “The Effect of Contact Time and pH on Methylene Blue removal by Volcanic Ash”, International Conference on Chemical, Biological and Environmental Sciences (ICCBES’14), May 12 – 13, Kuala Lumpur (Malaysia) 7. Sharma A. and Bhattacharya K. G., (2005), “Utilization of a Biosorbent based on Azadirachtaindica(Neem) Leaves for Removal of Water- Soluble Dyes”, Indian Journal of Chemical Technology, Vol. 12, pp. 285 – 295. 8. Vinoth M., Lim H. Y., Xavier R., Marimuthu K., Sreeramanan S., Rosemal M. H. M. H. and Kathiresan S., (2010), “Removal of Methyl Orange from Solutions Using Yam Leaf Fibres”, International Journal of Chem Tech Research, Vol. 2, No. 4, pp 1892 – 1900.