Chemosphere, Vol.25, No. 11, pp 1691-1705, ! 992 0045-6535/92 $5.00 + 0.

00
Printed in Great Britain Pergamon Press Ltd.

WASTE BANANA PITH AS ADSORBENT FOR COLOR

REMOVAL FROM WASTEWATERS
C. Namasivayam* and N. Kanchana
Environmental Chemistry Division
Department of Environmental Sciences
Bharathiar University, Coimbatore - 641046
Tamil Nadu, India

(Received in USA 27 August 1991; accepled 4 September 1992)

ABSTRACT
The ability of waste banana pith to remove color from synthetic wastewaters
containing Acid violet, Congo red + Rhodamine B mixture and Congo red + Acid Violet
+ Rhodamine-B mixture was investigated. The influence of various parameters like dye
concentration, contact time, adsorbent dosage and pH on the removal of dyes has been
studied. The adsorption rate constant for Acid violet was found to be 1.27 x 10l/rain at
20 mg/L dye concentration. The equilibrium data for Acid violet fit well into Langmuir and
Freundlich isotherms. Maximum removal of 80% was observed for Acid violet at 50 mg/L
and at pH 2. Desorption studies reveal that the adsorption of Acid violet is mainly due to
chemisorption. Complete removal of dye mixture, Congo red + Rhodamine-B (20 mg/L
each) was observed at an adsorbent dosage of 6 g. The color removal was quantitative for
the dye mixtures, Congo red + Acid violet + Rhodamine-B (10 mg/L each) and Congo red
+ Acid violet + Rhodamine-B (20 mg/L each) by 5 and 6 g of adsorbent, respectively.
Key words: Waste banana pith, Acid violet, adsorption isotherms, intraparticle diffusion,
pH effect.

INTRODUCTION
Wastes from dye and textile industries pollute the surrounding water resources by
reducing the self purifying capacity of water bodies. Most of the dyes used in the textile

"To Whom all Correspondence should be addressed

"Present address: Department of Chemistry, University of Victoria, P.O. Box 3055, Victoria,
B.C., V8W 3P6, Canada

1691
1692

industry are stable to light and oxidation, as well as resistant to anaerobic digestion 1.
Although activated carbon is quite effective in the removal of dyes 2, a developing country
like India often cannot afford its high cost of procurement and regeneration. Various non-
conventional and low-cost adsorbents like chitin 3, fuller's earth and fired clay4, flyash5, china
clay6, peat moss and rice hulls 7, coconut husks, Fe3+/Cr 3 hydroxide sludge and red mud 9,
and biogas residual slurry 1'n'12 have been studied. In India, 80% of the population depends
on land for living, and utilization of agricultural wastes will provide additional employment
and income. India is the second ~argest banana producer after Brazil. India produces about
2.34 million tonnes from a cultivated area of 164,000 hectare 13. The central white portion
of the banana plant (pith) is used to treat persons bitten by poisonous snake ~4. Banana
stems are used for biogas generation is, paper making 16, ethanol production 17, etc. After
harvesting the banana "bunch" the rest of the plant is thrown away, burnt to reduce its
volume, or (rarely) used as manure. The approximate amount of dry matter produced per
banana plant is about 1, 1.3, and 5 g of leaf, pseudostem and fruits, respectively TM. In India
more than 200 million tonnes of agricultural wastes are produced annually 13. Such
agricultural wastes can be used for the treatment of wastcwaters economically. The
objective of this study is to investigate the capacity of waste banana pith to adsorb three
textile dyes, Acid violet (acid dye), Congo red + Rhodamine-B mixture and Congo red +
Acid violet + Rhodamine-B mixture.

MATERIALS AND METHODS

Banana stems were collected from a farm. The outer portion was removed and the
central white portion (Banana pith) was used for this investigation. The banana pith was
cut into pieces and dried in sunlight. The particle size of the sieved banana pith powder is
in the range of 53~m to 1ram. Acid violet and Congo red were supplied by Hindustan Ciba
Geigy, Bombay. Rhodamine-B was obtained from Atul, Bombay. Tap water was used for
the preparation of dye solutions. Batch adsorption experiments were carried out by agitating
the adsorbent with 100 mL aqueous solution of Acid violet of a desired initial concentration
at pH 8.56 for a predetermined time interval at 140 rpm using a shaker machine. The
residual dye was removed by centrifugation at 4700 g. The amount of dye adsorbed was
determined by monitoring the absorbances before and after treatment using Hitachi
 1693

Spectrophotometer (model U-3210). In the case of dye mixtures, wavelength of maximum

absorption (~max -- 553.8 nm) was used for the estimation of color removal. The effect of
adsorbent dosage on the removal of Acid violet was studied by varying adsorbent weight
from 0.25 to 3.00 g at the dye concentration of 50 mg/L at pH 7.74. The effect of adsorbent
dosage on the adsorption of Congo red + Rhodamine-B mixture (20 mg/L each) and Congo
red + Acid violet + Rhodamine-B mixture (10 mg/L each and 20 mg/L each) was
investigated by varying the adsorbent dosage from 0.5 to 6.00 g and 0.5 to 5.00 g,
respectively. The influence of pH on the removal of the dye was studied by adjusting the
pH of 50 mL dye solution (50 mg/L) and 50 mL of water containing 1 g adsorbent using 1:1
HC1 or dilute NaOH solutions to a desired value. After equilibration of pH, the dye
solution and the adsorbent slurry were mixed and agitated for an equilibrium time of 20
minutes. Desorption studies were conducted by shaking 1 g of used adsorbent containing
1.46 mg of Acid violet with 100 mL of various desorbing media like distilled water, 2N
sulphuric acid or 50% (v/v) acetic acid. Generally in the experiments, the dye concentration
was maintained at 20 mg/L, adsorbent at 1.0 g, agitation time at 20 min, pH at 8.56 and
temperature at 30 + 2C, unless otherwise stated.

RESULTS AND DISCUSSION

1. INTERACTION OF DYE AND ADSORBENT:
Since the aqueous extract of the adsorbent is also colored, absorbance correction is
required in the estimation of dye removal at different pH. Absorbance correction due to
extract can be given only when there is no chemical reaction between the dye and the
extract. In order to find out whether there is any chemical reaction between the dye and
the aqueous extract of waste banana pith, the following experiment was performed. 1 Fifty
milliliters of dye solution (20 mg/L) and aqueous extract (from 1 g banana pith in 50 mL
water) were prepared at different pH from 4.81 to 9.23. Absorbances were measured at
545.6 nm before and after mixing dye solutions and aqueous extracts. It was found that
there was no significant change in the absorbances in the pH range studied (Table 1). This
shows that there is no chemical reaction between the dye used and the aqueous extract of
waste banana pith 1. This enables one to give absorbance correction due to the extract in
the calculation of percent dye removal after treatment.
1694

U3

+ oo oo ~
d d c~ ~

7
U

"S
g
u3
-d- <
u3

<
-d" ~ (3~ -d" 0

c~ d d d c~

~J

[..
 1695

2. EFFECT OF CONTACT TIME AND INITIAL DYE CONCENTRATION:

The percent removal of Acid violet decreased from 73 to 57% when the
concentration of Acid violet increased from 20 to 200 mg/L, indicating that the dye removal
is dependent on initial concentration. The dye removal increased with the agitation time.
This may be attributed to a decrease in the diffusion layer thickness surrounding the
adsorbent particles 19. The equilibrium time increased with increasing dye concentration.
Similar results were reported in the removal of Acid violet by biogas waste slurry 11. The
percent removal vs time curves (Fig. 1) are single, smooth and continuous indicating the
formation of monolayer coverage on the outer surface of the adsorbent 2.

13 Q------J3---

~5

@:3

0--4:3---0 0 0 0 O'

I
60 1~o l&o 2~ ~o
t,min

Figure 1. Effect of agitation time and dye concentration on removal of Acid

violet by waste banana pith; dye concentration: ( O ) 20 rag/L, ( a ) 50 mg/L,
(<~) 75 mg/L and ( [] ) 100 mg/L.
1696

3. ADSORPTION DYNAMICS:
The adsorption rate constant of Acid violet on waste banana pith was obtained using
Lagergren rate equation 21.
K'
log(% - q) . log q~ 2.30~ t (1)

where qe and q are the amount of dye adsorbed (rag/g) at equilibrium and at time t, and
K' is the rate constant. The K' values were calculated from the slopes of the linear plots
of log (qe-q) vs t (Fig. 2) and are presented in Table II. Maximum K' value of 1.27 x
10"l/min was observed for dye concentration of 20 mg/L. The K' value for the adsorption
of Acid violet by biogas waste slurry has been reported as 1.3 x 10"~/min n.

~o
u

I I [ I I I
20 4,0 60 80 100 120 ~z~O ~1~3 180

t,rnin

Figure 2. Lagergren plot for the adsorption of Acid violet by waste banana
pith; dye concentration: ( ( ~ ) 20 mg/L~ ( A ) 50 rag/L, ( D ) 75 m g / L and
(~:~) 100 mg/L.
 1697

Table II. Adsorption rate constants

Concentration, Rate constant, K'

mg/L min 1

20 0.127

50 0.037

75 0.025

100 0.018

4. INTRAPARTICLE DIFFUSION
According to Weber and Morris if the rate limiting step is intraparticle diffusion, a
plot of dye adsorbed (q) against square root of contact time (t ~) should yield a straight line
passing through the origin 4. These plots (Fig. 3) give straight lines at each concentration but
do not pass through the origin showing that the intraparticle diffusion is not the only rate
controlling stepS; 10-12. Similar results were reported in the removal of Acid violet by biogas
waste slurry 11. The rate constants of intraparticle diffusion (Kp) were calculated from the
slopes of the linear portion of the plots q vs t" for different dye concentrations and are
presented in Table III. Kp value for the adsorption of Acid violet by biogas waste slurry
was 1.08 x 10-1 mg/g/min" at a dye concentration of 50 mg/L n.

5. ADSORPTION ISOTHERMS
Langmuir Isotherm
The equilibrium results at different concentrations were analysed in the light of the
Langmuir equation 21

Ce/qe = 1/Qb + Ce/Q (2)

where Ce is the equilibrium concentration of the dye in solution (mg/L) and QO and b are
constants signifying the adsorption capacity and energy of adsorption, respectively. The
values of QO and b were calculated from slope and intercept of the straight line plot of
1698

i i . J
0 4 8 12 - - 16

tl/2,m;1/2
Figure 3. Amount of dye adsorbed (rag dye/g adsorbent) vs t ~ for the
intraparticle transport of Acid violet by waste banana pith; dye concentration:
( O ) 20 mg/L, ( a ) 50 mg/L, ( ;-I ) 75 mg/L and (:~) 100 mg/L.

Table III. Rate constants for intraparticle diffusion

Concentration, Rate constant, Kp

mg/L Mg/g/min ~

20 0.082

50 0.065

75 0.076

100 0.108
 1699

Ce/qe vs Ce (Fig. 4) and are given in Table IV. The applicability of Langmuir isotherm for
Acid violet on waste banana pith (Fig. 4) indicates monolayer adsorption on a surface
containing a finite number of identical sites and is in good agreement with previous
findings u.
The essential characters of Langrnuir Isotherm can be expressed by a dimensionless
constant called equilibrium parameter, R L which is defined byz

R E . 1/(1 + bCo) (3)

R E values between 0 and 1 indicate (Table IV) favourable adsorption for Acid violet on
waste banana pith 2.

Freundlich Isotherm
Freundlich isotherm is represented by the equation 5
log(x/m) . logk + 1/n(logCe) (4)
where x is the amount of dye adsorbed (mg/L), m is the weight of the adsorbent used (g/L),
Ce is the equilibrium concentration of dye in solution (mg/L) and k and n are constants
incorporating all factors affecting the adsorption process such as adsorption capacity and
intensity of adsorption respectively. The percent removal of the Acid violet increased from
27 to 88% with increasing adsorbent dose from 0.25 to 3.00 g. Linear plots for log(x/m) vs
(log Ce) (Fig. 5) shows that the adsorption of Acid violet on banana pith also follows
Freundlich isotherm, k and n were calculated from the intercept and sl09e ~anal were 0.50
and 1.79, respectively. Values of k and n for the adsorption of Lanasyn black on rice hulls 17
and Acid violet on biogas waste slurry u have been reported as 0.63 and 1.59, and 1.17 and
1.42, respectively. Values of 1< n < 10 represents beneficial adsorption 3.

6. EFFECT OF pH
The removal of Acid violet by waste banana pith decreased from 80 to 48%, as the
pH of dye solution (50 mg/L) increased from 2.0 to 11.0 (Fig. 6). The favourable
adsorption at acidic pH is in accordance with the earlier reports on the removal of Acid
violet by biogas waste slurry 11.
1700

8

7 /
/
/
/

6
/
/

0
3

1~ 2~ 3'0 ~o ~'o
Ce,mg/L

Figure 4. Langmuir plot for the adsorption of Acid violet by waste banana
pith.

Table IV. Analysis of Langmuir Isotherm

QO b, Initial dye RL
mg/g L/rag concentration, Co,
mg/L

13.10 0.20 20 0.7143

50 0.5000

75 0.4000

100 0.3333
 1701

+1

:E
x

o'.2 o!4 o'-s o18 1:o 1!2 ~ 1%

Log Ce

Figure 5. Freundlich plot for adsorption of Acid violet by waste banana pith.

c~
E

o
2

L 6 ~2
pH

Figure 6. Removal of Acid violet by waste banana pith as a function of pH

(rag dye adsorbed per g vs pH). Dye concentration, 50 mg/L.
1702

7. DESORPTION STUDIES:
The occurrence of physisorption and ion exchange was ruled out by a very low
desorption of 5.00 and 1.67% with distilled water and sulphuric acid, respectively. Maximum
desorption of 70% was observed with 50%(v/v) acetic acid. This indicates the occurrence
of chemisorption. Similar results were reported for the desorption of Acid violet from the
dye adsorbed-biogas waste slurry ~1.

8. REMOVAL OF DYE MIXTURES:

a) Effect of agitation time
The percent removal of dye mixture increased with agitation time for both the dye
mixtures, Rhodamine-B + Congo red and Congo red + Acid violet + Rhodamine-B and
an equilibrium time of 40 minutes was observed for the dye mixtures used (Fig. 7). A
maximum removal of 73% was observed for Rhodamine-B + Congo red mixture at 20 mg/L
each. The percent removal was nearly the same (77%) for Congo red + Acid violet +
Rhodamine-B mixture at 10 mg/L each and 20 mg/L each.

100

80 ~ [3 ~
o -o---

60

20
I I I I I I I
40 80 120 160 200 240 280

tmln

Figure 7. Effect of Agitation time on the removal of dye mixture by waste

banana pith. Dye concentration: ( C ) ) Congo red + Rhodamine-B mixture
(20 mg/L each), ( A ) Congo red + Acid violet + Rhodamine B mixture (10
mg/L each), ( [] ) Congo red + Acid violet + Rhodamine-B mixture (20
mg/L each)
 1703

b) Effect of adsorbent dosage

The percent removal of dye mixture increased with increasing adsorbent dosage (Fig.
8). Almost complete removal of Congo red + Rhodamine-B mixture (20 mg/L each) was
observed at an adsorbent dosage of 6 g. Complete removal of dye mixture was observed
for Congo red + Acid violet + Rhodamine-B mixture (10 mg/L each) by 5 g of adsorbent
and for Congo red + Acid violet + Rhodamine-B mixture (20 mg/L each) by 6 g of
adsorbent.

100

80

6(]
~o
E
~. 4o

2o

I I ~ _ _ 1 1 I
] 2 3 4 5 6

Adsorb~n[dosog~ , ~/lae mL

Figure 8. Effect of adsorbent dosage on the removal of dye mixtures by Waste

banana pith. Dye concentration: ( ( ~ ) Congo red + Rhodamine-B mixture
(20 mg/L each), ( A ) Congo red + Acid violet + Rhodamine-B mixture (10
mg/L each), ( [] ) Congo red + Acid violet + Rhodamine-B mixture (20
mg/L each).

CONCLUSION
The waste banana pith is an effective adsorbent for the removal of Acid violet,
Congo red + Rhodamine-B mixture and Congo red + Acid violet + Rhodamine-B mixture.
Therefore it can be used for the treatment of dyeing wastewaters enriched with the above
dyes. Since the treated water contains only the extract of banana pith, it can be used for
irrigational purposes.

ACKNOWLEDGEMENT
Authors are thankful to Mrs. Carol Olson of the University of Victoria for the
preparation of the manuscript.
1704

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