Professional Documents
Culture Documents
Use of agricultural waste sugar beet pulp for the removal of Gemazol
turquoise blue-G reactive dye from aqueous solution
Zümriye Aksu ∗ , I. Alper Isoglu
Hacettepe University, Department of Chemical Engineering, 06532 Beytepe, Ankara, Turkey
Received 30 November 2005; received in revised form 16 February 2006; accepted 16 February 2006
Available online 6 March 2006
Abstract
The potential use of dried sugar beet pulp, an agricultural solid waste by-product, as an biosorbent for Gemazol turquoise blue-G, a
copper–pthalocyanine reactive dye commonly used in dyeing of cotton, was investigated in the present study. Batch adsorption studies were
carried out to examine the influence of various parameters such as initial pH, temperature and initial dye concentration. The results indicated
that adsorption was strongly pH-dependent and slightly temperature-dependent. At 800 mg l−1 initial Gemazol turquoise blue-G concentration,
dried sugar beet pulp exhibited the highest Gemazol turquoise blue-G uptake capacity of 234.8 mg g−1 at 25 ◦ C and at an initial pH value of
2.0. The Freundlich, Langmuir, Redlich–Peterson and Langmuir–Freundlich, the two and three parameters adsorption models were used for the
mathematical description of the biosorption equilibrium and isotherm constants were evaluated depending on temperature. Both the Langmuir and
Redlich–Peterson models were applicable for describing the dye biosorption by dried sugar beet pulp in the concentration (100–800 mg l−1 ) and
temperature (25–45 ◦ C) ranges studied. Simple mass transfer and kinetic models were applied to the experimental data to examine the mechanisms
of biosorption and potential rate controlling steps such as external mass transfer, intraparticle diffusion and biosorption process. The sorption
process was found to be controlled by both surface and pore diffusion with surface diffusion at the earlier stages followed by pore diffusion at
the later stages. Pseudo first-order, pseudo second-order and saturation type kinetic models described the biosorption kinetics accurately at all
concentrations and temperatures studied. The thermodynamic analysis indicated that the sorption process was exothermic and the biosorption of
dye on dried sugar beet pulp might be physical in nature.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Agricultural waste; Biosorption; Gemazol turquoise blue-G; Reactive dye; Dried sugar beet pulp; Kinetics; Isotherms
1. Introduction are either toxic or mutagenic and carcinogenic due to the pres-
ence of metals and other chemicals, in their structure. Colour
Because of their ease of use, inexpensive cost of synthesis, removal has been the subject of increased attention in the last
stability and variety of colours compared with natural dyes, syn- few years. Reactive dyes are typically azo-based chromophores
thetic dyestuffs have been increasingly used in the textile, paper, combined with different types of reactive groups. They differ
rubber, plastics, cosmetics, pharmaceutical and food industries. from all other classes of dyes in that they bind to the textile
Today there are more than 10,000 dyes available commercially, fibres such as cotton to form covalent bonds. They have the
most of which are difficult to biodegrade due to their com- favourable characteristics of bright colour, water-fast, simple
plex aromatic molecular structure and synthetic origin [1,2]. application techniques and low energy consumption and are
The extensive use of dyes often poses pollution problems in used extensively in textile industries, but nearly 50% of reac-
the form of coloured wastewater discharge into water bodies. tive dyes may be lost to the effluent after dyeing of cellulose
Even small quantities of dyes can colour large water bodies; fibres. Reactive dyes cannot be easily removed by conventional
colour not only affects aesthetic quality but also reduces sun- wastewater treatment systems since they are stable to light, heat
light penetration and photosynthesis. In addition, some dyes and oxidizing agents and are biologically non-degradable so they
have been, therefore, identified as problematic compounds in
textile effluents. Hence, their removal is of great importance
∗ Corresponding author. Tel.: +90 312 2977434; fax: +90 312 2992124. [3–6]. Among the reactive dyes, copper–phthalocyanine dyes
E-mail address: zaksu@hacettepe.edu.tr (Z. Aksu). like Gemazol turquoise blue-G are preferred to direct dyes due
0304-3894/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2006.02.019
Z. Aksu, I.A. Isoglu / Journal of Hazardous Materials B137 (2006) 418–430 419
This study presents the first outcoming results about the pos- initial pH value did not change considerably during the experi-
sible use of the agricultural solid waste of dried sugar beet pulp mental period.
as Gemazol turquoise blue-G reactive dye biosorbent as a func-
tion of initial pH, temperature and initial Gemazol turquoise 2.3. Sorption studies
blue-G concentration. This material was chosen considering its
large amount availability and the basic cellulosic structure, rich Sorption studies were conducted in a routine manner by the
of possible binding active sites. Although a large number of pub- batch technique. A number of stoppered Pyrex glass Erlen-
lications have recently suggested using raw or activated sugar meyers containing a definite volume (100 ml in each case) of
beet pulp for removing heavy metal ions from aqueous solutions, solutions of Gemazol turquoise blue-G dye of desired concen-
there seems to be no study which reports all the equilibrium, tration, pH and temperature were placed in a thermostatic rotary
kinetic and thermodynamic modelling of Gemazol turquoise shaker. For the studies, 0.1 g of biosorbent was treated with
blue-G reactive dye adsorption due to temperature by dried sugar 100 ml of dye bearing solution. The flasks were agitated at a
beet pulp in a batch system, which are important in the design 150 rpm constant shaking rate for 24 h to ensure equilibrium was
of treatment processes in a wide range of dye concentration. reached. Samples (5 ml) were taken before mixing the biosorbent
and dye bearing solution and at pre-determined time intervals.
2. Materials and methods The dye solution was separated from the biosorbent by centrifu-
gation (Nuve, TURKEY) at 5000 rpm for 5 min. Uptake values
2.1. Adsorbent were determined as the difference between the initial dye con-
centration and the one in the supernatant. All the experiments
In this study, the waste pulp of sugar beet remaining from were carried out in duplicates and the average values were used
extraction of sugar was used as dye biosorbent. The pulp for further calculations.
was obtained from the Ankara Sugar Mill, Turkey. The col-
lected biomaterial was extensively washed with tap water to 2.4. Analysis of Gemazol turquoise blue-G
remove soil and dust, sprayed with distilled water and then
dried in an oven at 100 ◦ C to a constant weight. After grind- The concentration of unadsorbed Gemazol turquoise blue-G
ing and dry sieving, three particle sizes were kept: 250, 350 and dye in the biosorption medium were measured colorimetrically
500 m. using a spectrophotometer (Bausch and Lomb-Spectronic 20D,
The adsorbent particle size is an important factor in adsorp- Milton Roy Company, USA). The absorbance of the colour was
tion kinetics because it determines the time required for transport read at 341 nm.
of sorbate within the pore to adsorption sites. The diffusional
resistance to mass transfer is greater for large particles but, the 3. Results and discussion
smallest size allows very fast removal kinetics if the adsorption
is to be primarily a surface phenomenon. Moreover, increas- Analysis of biosorption data is important for developing
ing the surface area due to small particle size also increases the equilibrium, kinetic and thermodynamic equations that can be
number of sites, or indirectly increases the adsorption capacity. used for design purposes. The equilibrium, kinetic and ther-
The preliminary batch biosorption experiments were carried out modynamic results obtained in the biosorption of Gemazol
using the three different beet pulp particle sizes of 250, 350 and turquoise blue-G on to dried sugar beet pulp are given as the
500 m. Since the <250 m particle size dramatically decreased units of adsorbed dye quantity per gram of adsorbent at any
the effectiveness of beet pulp for dye removal, the adsorbent time and at equilibrium [q = (C0 − C)/X and qeq = (C0 − Ceq )/X]
particle size of 250 m was selected for adsorption studies due (q; qeq : mg g−1 ), respectively, unadsorbed dye concentration
to its higher adsorption rate and capacity. Higher removal with in solution at any time and at equilibrium (C; Ceq : mg l−1 ),
smaller particle size also indicated that the dye biosorption was respectively, adsorbed dye concentration in solution at equilib-
a surface phenomenon. rium (Cad,eq : mg l−1 ) and biosorption yield (Ad% = 100 × (C0 −
Ceq )/C0 ).
2.2. Chemicals
3.1. Effect of initial pH on Gemazol turquoise blue-G
The test solutions containing Gemazol turquoise blue-G dye biosorption
were prepared by diluting 1.0 g l−1 of stock solution of dye
which was obtained by dissolving weighed quantity of Gemazol An important influencing factor for dye biosorption on
turquoise blue-G, a copper–phthalocyanine reactive dye (Colour agricultural by-products has been referred to pH as in most
index name: Reactive Blue 21; molecular weight; 576.1; purity: studies published in the literature. The variation of equilibrium
not specified) (supplied from GEMSAN, TURKEY), in 1 l of dye uptake with initial pH is given in Fig. 1 for an initial
double-distilled water. The range of concentrations of prepared dye concentration of 100 mg l−1 at 25 ◦ C for a contact time
dye solutions changed between 50 and 800 mg l−1 . The pH of of 24 h. As seen from the figure, the biosorption of Gemazol
each solution was adjusted to the required value with diluted turquoise blue-G was maximum at pH 2.0 (qeq = 83.7 mg g−1 )
or concentrated H2 SO4 and NaOH solutions before mixing the and declined sharply with further increase in pH and reached to
biomass suspension. The preliminary studies showed that the zero at pH 6, so the working pH value for Gemazol turquoise
Z. Aksu, I.A. Isoglu / Journal of Hazardous Materials B137 (2006) 418–430 421
Table 1
Effect of initial Gemazol turquoise blue-G dye concentration and temperature on the equilibrium uptake capacity and biosorption yield of dried sugar beet pulp
25 ◦ C 35 ◦ C 45 ◦ C
C0 (mg l−1 ) qeq (mg g−1 ) Ad% C0 (mg l−1 ) qeq (mg g−1 ) Ad% C0 (mg l−1 ) qeq (mg g−1 ) Ad%
Table 2
Comparison of the Freundlich, Langmuir, Redlich–Peterson and Langmuir–Freundlich adsorption constants of Gemazol turquoise blue-G biosorption by dried sugar
beet pulp at different temperatures
Temperature (◦ C) KF (mg g−1 )(mg l−1 )−1/n ) n ε (%)
Freundlich model
25 20.02 2.40 11.98
35 15.89 2.26 4.57
45 11.43 2.05 6.86
Langmuir model
25 256.4 0.020 1.98
35 250.0 0.017 3.35
45 238.1 0.012 1.82
Redlich–Peterson model
25 0.018 4.71 1.000 1.98
35 0.020 3.88 0.960 3.17
45 0.011 2.64 1.000 1.88
Langmuir–Freundlich
25 2.14 0.0086 1.202 1.74
35 1.89 0.0074 1.088 2.75
45 1.89 0.0079 1.091 8.13
and an exponential function in the denominator. ysis and listed in Table 2 along with the average percentage
errors. The average percentage errors between the experimental
KRP Ceq
qeq = β
(3) and predicted values are calculated using Eq. (5). In Eq. (5), the
1 + aRP Ceq subscripts ‘exp’ and ‘calc’ show the experimental and calculated
values and N the number of measurements.
where KRP , aRP and β are the Redlich–Peterson parameters. The
N
exponent β lies between 0 and 1. For β = 1 Eq. (3) converts to |(qeq,i,exp − qeq,i,calc )/qeq,i,exp |
the Langmuir form [29]. ε (%) = i=1 × 100 (5)
N
Langmuir–Freundlich model is another three-parameter
empirical model for the representing equilibrium biosorption Fig. 4 also depicted the comparison of experimental and pre-
data. It is a combination of the Langmuir and Freundlich dicted qeq values obtained from these adsorption models at the
isotherm type models and is given by: temperatures of 25, 35 and 45 ◦ C. Basically, if most of the data
are distributed around the 45◦ line, this indicates that the model
m
ACeq
qeq = (4)
1 + BCeq
m
Table 3
Effect of initial Gemazol turquoise blue-G concentration and temperature on the external mass transfer coefficients (kL ) and intraparticle diffusion rate constants (K)
25 ◦ C 35 ◦ C 45 ◦ C
adsorption stage, where the intraparticle diffusion is rate-limited. t0.5 plots are also tabulated in Table 3. These are rate parameters
The third portion is final equilibrium stage where the intraparti- with units mg g−1 min−0.5 and as such, are not a direct quan-
cle diffusion starts to slow down due to extremely low solute tification of the rates. Nevertheless, they can be interpreted in
concentration in the solution and surface. A good correlation of relative terms. Examined in this way, the data show the rate of
rate data in this model can justify the mechanism and K-values diffusion increased with a raise in initial dye concentration and
can be obtained by linearizing the curve q = f (t0.5 ). decreased with increasing temperature of solution. This may be
Fig. 7 shows the effect of initial dye concentration and tem- due to a greater driving force with increasing C0 . Increasing the
perature on intraparticular diffusion at 100 and 800 mg l−1 initial dye concentration in the solution promoted the diffusion in the
Gemazol turquoise blue-G concentrations and at 25, 35 and particles. At all temperatures when C0 is increased from 50 to
45 ◦ C temperatures. As seen from the figure all the plots have the 400 mg l−1 there is a marked effect on the rate of intraparticu-
same general feature presenting multilinearity, indicating that a lar dye diffusion. Above C0 400 mg l−1 the effect is small. It is
few steps took place. The first, sharper portion which extent is also observed that the higher the value of K the more rapid is the
related to initial dye concentration, is attributed to the diffu- uptake of Gemazol turquoise blue-G dye. The linear plots at each
sion of adsorbate through the solution to the external surface of concentration and temperature did not pass through the origin
adsorbent or the boundary layer diffusion of solute molecules. and this indicated that the intraparticle diffusion is not only rate
The second linear portion describes the gradual layer adsorption controlling step. Moreover, according to the theoretical equa-
stage, where intraparticle diffusion is rate limiting. The third por- tions for diffusion, when intraparticle diffusion is the only rate
tion is attributed to the final equilibrium stage. At a certain time determining step, the rate parameter is also directly related to the
limit (between 5–60 min at all initial dye concentrations and at square root of the initial concentration (C00.5 ). Such a plot given
all temperatures studied) the curves revealed a linear characteris- in Fig. 8 also confirmed that intraparticle diffusion is not the only
tic. The values of K evaluated from these linear parts of q versus operative mechanism. These two results show that increasing the
Gemazol turquoise blue-G concentration in the solution seems
to reduce the diffusion of dye anions in the boundary layer and
to enhance the diffusion in the solid.
On the other hand, three simplified kinetic models including
pseudo first-order [32], pseudo second-order [33] and saturation
Fig. 7. q vs. t0.5 plots obtained at 100 and 800 mg l−1 initial Gemazol turquoise
blue-G concentrations and at different temperatures (initial pH 2.0, X: 1.0 g l−1 ,
agitation rate: 150 rpm). Fig. 8. Variation of K with C00.5 with respect to temperature.
Z. Aksu, I.A. Isoglu / Journal of Hazardous Materials B137 (2006) 418–430 427
type [30] were used to test the biosorption kinetics. These three
models basically include all steps of adsorption such as external
film diffusion, adsorption, and internal particle diffusion, so they
are pseudo-models.
The pseudo first-order rate expression based on solid capacity
is generally expressed as follows:
dq
= k1,ad (qeq − q) (10)
dt
where k1,ad is the rate constant of first-order biosorption. After
integration and applying boundary conditions, t = 0 to t = t and
q = 0 to q = qeq ; the integrated form of Eq. (10) becomes:
k1,ad
log(qeq − q) = log qeq − t (11)
2.303
A straight line of log(qeq −q) versus t suggests the applicabil- Fig. 9. Variation of rad with C0 with respect to temperature.
ity of this kinetic model. In most cases, the first-order equation
of Lagergren does not fit well for the whole range of contact where kad is the first-order rate constant of saturation type
time and is generally applicable over the initial 20–30 min of biosorption. The zero-order rate constant (k0 ,ad ) is expressed
the sorption process in the region where rapid sorption takes and Eq. (15) becomes:
as kad /kad
place.
The pseudo second-order equation is also based on the sorp- kad C0
rad = (16)
tion capacity of the solid phase and on the assumption that 1 + k0,ad C0
the sorption process involves chemisorption mechanism and is
expressed as: A straight line of 1/rad versus 1/C0 suggests the applicabil-
ity of this kinetic model and kad and k0,ad can be determined
dq from the slope and intercept of the plot. This model predicts the
= k2,ad (qeq − q)2 (12)
dt biosorption behavior over the whole studied concentration range
where k2 ,ad is the rate constant of second-order biosorption. For of dye at a constant temperature.
the same boundary conditions the integrated form of Eq. (12) The validity of all models can be checked from the linear
becomes plots.
The pseudo first-order rate constant (k1,ad ) and qeq values
t 1 1 were determined from the plots of linearized form of the pseudo
= 2
+ t (13)
q k2,ad qeq qeq first-order model (Eq. (11)) at all concentrations and at all tem-
peratures studied for the initial 30 min (data not shown) and
If second-order kinetics are applicable, the plot of t/q against are presented in Table 4 along with the corresponding correla-
t of Eq. (13) should give a linear relationship, from which qeq tion coefficients. The first-order rate constants decreased slightly
and k2 ,ad can be determined from the slope and intercept of the with increasing both the initial concentration of dye and tem-
plot and there is no need to know any parameter beforehand. perature. As seen from the table, besides very high regression
The applicability of saturation type kinetics in modeling the coefficients (>0.995), experimental qeq values agreed very well
kinetic data was also discussed. The plot of q versus time can be with qeq values obtained from Lagergren plots. This indicated
used to find the initial biosorption rate (rad ) by differentiating that pseudo first-order kinetic model describes the kinetics ade-
the plot at t = 0 as defined in Eq. (14). quately in the concentration and temperature ranges studied.
Using Eq. (13), t/q was plotted against t at 25, 35 and 45 ◦ C,
dq
= rad (14)
dt t=0 and second-order adsorption rate constants (k2,ad ) and equilib-
rium uptake values (qeq ) were determined from the slope and
From experimental data, it was shown that the initial biosorp- intercept of the plots (data not shown). The values of the param-
tion rate is proportional to the first power of the initial dye con- eters k2,ad and qeq and of corresponding correlation coefficients
centration at lower bulk dye concentrations (first-order kinetics) are also presented in Table 4. The results indicated that second-
and at higher dye concentrations, the rate becomes independent order rate constants were also affected by both the initial dye
of initial dye concentration (zero-order kinetics) (Fig. 9). Eq. concentration and temperature and diminished with increasing
(15) can be used to describe the rate of biosorption very accu- these parameters. The correlation coefficients of all temperatures
rately in both situations. This kind of rate equation is defined as and concentrations studied were also found very high and equal
‘saturation type’. to 1.000 in this case. Moreover the theoretical qeq values found
from the second-order kinetic model also agreed very well with
kad C0
rad = C (15) the experimental qeq values. This showed that the adsorption
1 + kad 0 of Gemazol turquoise blue-G also follows the pseudo-second-
428 Z. Aksu, I.A. Isoglu / Journal of Hazardous Materials B137 (2006) 418–430
Table 4
Comparison of the first- and second-order reaction rate constants and experimental and calculated qeq values obtained at different initial Gemazol turquoise blue-G
concentrations and temperatures
Temperature (◦ C) C0 (mg l−1 ) qeq,exp (mg g−1 ) First-order kinetic model Second-order kinetic model
k1,ad (×102 min−1 ) qeq,cal (mg g−1 ) R2 k2,ad (×103 g mg−1 min−1 ) qeq,cal (mg g−1 ) R2
order kinetic model. The values confirm that the sorption data the initial Gemazol turquoise blue-G concentration, temperature
are well represented by pseudo second-order kinetics for the and time.
entire sorption period suggesting chemisorption mechanism.
The saturation type kinetic model was also applied to the 3.7. Thermodynamic parameters of biosorption
experimental data at different temperatures changing from 25 to
45 ◦ C to describe the batch biosorption kinetics over the whole The thermodynamic parameters reflect the feasibility and
concentration range of dye studied. The values of kad and k0,ad spontaneous nature of the process. Thermodynamic parameters
were determined from the plots of linearized form of the satura- of free energy change, enthalpy change and entropy change can
tion type kinetic model at all temperatures (data not shown). be estimated using equilibrium constants changing with temper-
The plots indicated that such saturation type kinetic expres- ature. The biosorption process of Gemazol turquoise blue-G dye
sion is also so valid to the present system (R2 > 0.997 for all can be summarized by the following reversible process which
temperatures). Table 5 shows that both the biosorption rate con- represents a heterogeneous equilibrium.
stants were affected with increase in temperature and decreased
notably with increasing temperature. dye in solution ↔ dye − biosorbent (17)
These suggest that the biosorption of Gemazol turquoise
The apparent equilibrium constant (Kc ) of the biosorption is
blue-G at 25, 35 and 45 ◦ C may be best described by the pseudo
defined as:
first-order and pseudo second-order kinetics, following satura-
tion type kinetic model, with fairly high correlation coefficients. Cad,eq
Kc = (18)
The change of rate constant due to temperature also showed that Ceq
one of the rate controlling steps is biosorption reaction. Apply-
ing the Weber and Morris principles to the variation in the initial where Cad,eq is the concentration of dye on the biosorbent at
rate with C0 (Fig. 9) indicated that the rate was not directly pro- equilibrium. In this case the activity should be used instead of
portional to C0 and also confirmed that sorption process was concentration in order to obtain the standard thermodynamic
not the only rate limiting step. The data also confirmed that both equilibrium constant (Kc0 ) of the biosorption system. If infinite
mass transfer and pore diffusion are important in determining the dilute value of Kc can be found by calculating the apparent
biosorption rates and that their relative significance depends on equilibrium constant (Kc ) at different initial concentrations of
dye and extrapolating to zero, this value will give Kc0 . When
Table 5 1 g l−1 of adsorbent is used, this value can be taken equal to the
Comparison of the saturation type kinetic rate constants obtained at different opposite value of intercept of Ceq /qeq versus Ceq plot (=bQ◦ ),
temperatures which shows the linearized form of Langmuir equation. The Kc0
Temperature (◦ C) kad (×102 l g−1 min−1 ) k0,ad (×102 l mg−1 ) R2 value is used in the following equation to determine the free
energy change of the biosorption reaction (Gibbs free energy)
25 3.30 0.35 0.989
(G◦ ) at 25 ◦ C.
35 2.66 0.32 0.998
45 1.95 0.26 0.994
G◦ = −RT ln Kc0 (19)
Z. Aksu, I.A. Isoglu / Journal of Hazardous Materials B137 (2006) 418–430 429
where R the universal gas constant and T the absolute tempera- [34] examined the biosorption of Remazol turquoise blue-G by
ture. The free energy change indicates the degree of spontane- non-living K. marxianus IMB3 yeast and found a 98.0 mg g−1
ity of the biosorption process and the higher negative value maximum dye uptake capacity. Kargi and Ozmihci [35] studied
reflects a more energetically favourable adsorption. The equi- the biosorption of the same reactive dye with powdered acti-
librium constant may be expressed in terms of enthalpy change vated sludge and powdered activated carbon and determined
of biosorption (H◦ ) and entropy change of biosorption (S◦ ) the maximum biosorption capacity of each sorbent as 92.0 and
as a function of temperature. The relationship between the Kc0 98.0 mg g−1 , respectively. Aksu and Sen Cagatay [7] studied
and temperature is given by the van’t Hoff equation with the dried fungus R. arrhizus for the biosorption of Gema-
zol turquoise blue-G; the biosorption capacity of biosorbent was
S ◦ H ◦
ln Kc0 = − (20) 625.0 mg g−1 at 45◦ . The comparison of results of this work with
R RT the others found in the literature showed that dried sugar beet
H◦ and S◦ can be obtained from the slope and intercept of a pulp has a significantly high adsorption capacity for G(R)emazol
van’t Hoff plot of ln Kc0 versus 1/T. turquoise blue-G dye.
The Kc0 value at 25 ◦ C evaluated from the Caq,eq /Ceq versus The adsorption process rate and dynamic behavior of the
Ceq plot (data not shown) as 5.12 was used to find the G◦ value. system are very important factors for the process design and
The standard Gibbs free energy for the biosorption process was operation control. A film diffusion model and an intraparticle
obtained as −4.05 kJ mole−1 using Eq. (19). A negative value diffusion model developed by Weber and Morris were used to
of G◦ confirms the feasibility of the process and spontaneous find both the boundary and intraparticle diffusion rate constants.
nature of biosorption at 25 ◦ C with a high degree of affinity Three simplified models including pseudo first-order, pseudo
of the dye molecules for the biomass surface. The standard second-order and saturation type kinetic models were also used
enthalpy and entropy changes of biosorption determined from to test the adsorption kinetics. It was shown that the adsorption
the ln Kc0 versus 1/T plot (R2 = 0.966) were −23.09 kJ mole−1 of Gemazol turquoise blue-G dye on to dried sugar beet pulp
and −0.064 kJ mole−1 K−1 , respectively. The negative value of at 25, 35 and 45 ◦ C is best described by all kinetic models with
H◦ indicates an exothermic biosorption reaction favorable at fairly high correlation coefficients with film and intraparticle
lower temperature while negative S◦ confirms the decreased diffusion being the essential rate controlling steps. The kinetic
randomness at the solid–solution interface during biosorption. parameters obtained can be used for reactor design.
Thermodynamic constants were also evaluated using equilib-
4. Conclusion rium constants changing with temperature. The negative value
of G◦ indicated the spontaneity and the negative values of H◦
An untried, low cost, locally available biosorbent was investi- and S◦ showed the exothermic nature and increase in order of
gated for its anionic dye removal capacity from aqueous solution. Gemazol turquoise blue-G biosorption, respectively.
Dried sugar beet pulp has been used successfully as an adsorb- Results obtained from this study showed that dried sugar beet
ing agent for the removal of Gemazol turquoise blue-G dye from pulp was very effective at removing Gemazol turquoise blue-G
aqueous solution. Adsorption was influenced by various parame- dye to very high concentrations from the aqueous solution in a
ters such as initial pH, temperature and initial dye concentration. static batch system. Since sugar beet pulp, an agricultural solid
The maximum uptake of Gemazol turquoise blue-G by dried waste, is freely, abundantly and locally available, the sorbent is
sugar beet pulp occurred at an initial pH of 2.0 and adsorp- expected to be economically viable for wastewater treatment.
tion increased with increasing Gemazol turquoise blue-G dye We believe that application of biosorption by dried sugar beet
concentration up to 800 mg l−1 and decreased with increasing pulp in purification of waste water for the removal of Gemazol
temperature from 25 to 45 ◦ C. turquoise blue-G from industrial wastewaters can be suitable for
Adsorption equilibrium data were correlated with the Lang- the fabrication and designing of wastewater treatment plants by
muir, Freundlich, Redlich–Peterson and Langmuir–Freundlich using these kinetic parameters.
isotherms depending on temperature and the Langmuir and
Redlich–Peterson models were found to provide the best fit of the References
experimental data in the concentration and temperature ranges
studied. Assuming the batch adsorption as a single-staged equi- [1] E.A. Clarke, R. Anliker, Organic dyes and pigments, in: Handbook
librium operation, the separation process can be mathematically of Environmental Chemistry Anthropogenic Compounds, Springer, New
defined using these isotherm constants to estimate the residual York, 1980.
concentration of Gemazol turquoise blue-G or amount of adsor- [2] H. Zollinger, Color Chemistry––Synthesis Properties and Applications
of Organic Dyes and Pigments, VCH, New York, 1987.
bent for desired purification. [3] L.C. Morais, O.M. Freitas, E.P. Gonçalves, L.T. Vasconcelos, C.G. Gon-
According to the Langmuir model, the maximum dye zalez Beça, Reactive dyes removal from wastewaters by adsorption on
biosorption capacity of biosorbent was 256.4 mg g−1 at 25 ◦ C. eucalyptus bark: variables that define the process, Water Res. 33 (1999)
The Gemazol turquoise blue-G adsorption capacity of dried 979–988.
[4] I. Arslan, I. Akmehmet Balcioglu, Degradation of commercial reactive
sugar beet pulp was compared to the adsorption capacities of
dyestuffs by heterogenous and homogenous advanced oxidation pro-
some other adsorbents reported in literature. Differences of cesses: a comparative study, Dyes Pigments 43 (1999) 95–108.
dye uptake are due to the properties of each adsorbent such [5] T. Robinson, G. McMullan, R. Marchant, P. Nigam, Remediation of
as structure, functional groups and surface area. Bustard et al. dyes in textile effluent: a critical review on current treatment technolo-
430 Z. Aksu, I.A. Isoglu / Journal of Hazardous Materials B137 (2006) 418–430
gies with a proposed alternative, Bioresource Technol. 77 (2001) 247– [21] R. Gong, Y. Ding, M. Li, C. Yang, H. Liu, Y. Sun, Utilization of
255. powdered peanut hull as biosorbent for removal of anionic dyes from
[6] Z. Aksu, Application of biosorption for the removal of organic pollu- aqueous solution, Dyes Pigments 64 (2005) 187–192.
tants: a review, Process Biochem. 40 (2005) 997–1026. [22] M. Arami, N.Y. Limaee, N.M. Mahmoodi, N.S. Tabrizi, Removal of
[7] Z. Aksu, S. Sen Cagatay, Investigation of biosorption of Gemazol dyes from colored textile wastewater by orange peel adsorbent: equi-
turquoise blue-G reactive dye by dried Rhizopus arrhizus in batch and librium and kinetic studies, J. Colloid Interface Sci. 288 (2005) 371–
continuous systems, Sep. Pur. Technol. 48 (2006) 24–35. 376.
[8] Y.M. Slokar, A.M. Le Marechal, Methods of decoloration of textile [23] V.M. Dronnet, C.M.G.C. Renard, M.A.V. Axelos, J.-F. Thibault, Binding
wastewaters, Dyes Pigments 37 (1997) 335–356. of divalent metal cations by sugar-beet pulp, Carbohydrate Polym. 34
[9] C. Namasivayam, K. Kadirvelu, Coir pith as an agricultural waste by- (1997) 73–82.
product, for the treatment of dyeing wastewater, Bioresource Technol. [24] C. Gerente, P. Couespel du Mesnil, Y. Andres, J.-F. Thibault, P. Le
48 (1994) 79–81. Cloirec, Removal of metal ions from aqueous solution on low cost
[10] Y. Fu, T. Viraraghavan, Fungal decolorization of wastewaters: a review, natural polysaccharides: sorption mechanism approach, Reactive Funct.
Bioresource Technol. 79 (2001) 251–262. Polym. 46 (2000) 135–144.
[11] G. McKay, G.R. Prasad, P.R. Mowli, Equilibrium studies for the adsorp- [25] V.K. Gupta, I. Ali, Utilisation of bagasse fly ash (a sugar industry waste)
tion of dyestuff from aqueous solutions by low-cost materials, Water Air for the removal of copper and zinc from wastewater, Sep. Pur. Technol.
Soil Pollut. 29 (1986) 273–283. 18 (2000) 131–140.
[12] S.S. Nawar, H.S. Doma, Removal of dyes from effluents using low-cost [26] Z. Aksu, I.A. Isoglu, Removal of copper(II) ions from aqueous solution
agricultural by-products, Sci. Total Environ. 79 (1989) 271–279. by biosorption onto agricultural waste sugar beet pulp, Process Biochem.
[13] P. Nigam, G. Armour, I.M. Banat, D. Singh, R. Marchant, Physical 40 (2005) 3031–3044.
removal of textile dyes and solid state fermentation of dye-adsorbed [27] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica,
agricultural residues, Bioresource Technol. 72 (2000) 219–226. and platinum, J. Am. Chem. Soc. 40 (1918) 1361–1368.
[14] C.B. Chandran, D. Singh, P. Nigam, Remediation of textile effluent using [28] H. Freundlich, Adsorption in solution, Phys. Chem. Soc. 40 (1906)
agricultural residues, Appl. Biochem. Biotechnol. 102 (2002) 207–212. 1361–1368.
[15] G. Annadurai, R.-S. Juang, D.-J. Lee, Use of cellulose-based wastes for [29] O.J. Redlich, D.L. Peterson, A useful adsorption isotherm, J. Phys.
adsorption of dyes from aqueous solutions, J. Hazard. Mater. 92 (2002) Chem. 63 (1959) 1024.
263–274. [30] Z. Aksu, E. Kabasakal, Batch adsorption of 2,4-dichlorophenoxy-acetic
[16] G. McKay, M. El Geundi, M.M. Nassar, Equilibrium studies for the acid (2,4-D) from aqueous solution by granular activated carbon, Sep.
adsorption of dyes on bagasse pitch, Adsorption Sci. Technol. 15 (1997) Pur. Technol. 35 (2004) 223–240.
251–270. [31] W.J. Weber, J.C. Morris, Kinetics of adsorption on carbon from solution,
[17] S.D. Khattri, M.K. Singh, Colour removal from dye wastewater using J. Sanit. Eng. Div. Am. Soc. Civ. Eng. 89 (1963) 31–39.
sugar cane dust as an adsorbent, Adsorption Science Technol. 17 (1999) [32] S. Lagergren, Zur theorie der sogenannten adsorption gelöster stoffe,
269–282. Kungliga Svenska Vetenskapsakademiens, Handlingar 24 (1898) 1–
[18] T. Robinson, B. Chandran, P. Nigam, Removal of dyes from an artifi- 39.
cial textile dye effluent by two agricultural waste residues, corncob and [33] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes,
barley husk, Environ. Int. 28 (2002) 29–33. Process Biochem. 34 (1999) 451–465.
[19] P.K. Malik, Use of activated carbons prepared from sawdust and rice- [34] M. Bustard, G. McMullan, A.P. McHale, Biosorption of textile dyes by
husk for adsorption of acid dyes: a case study of Acid Yellow 36, Dyes biomass derived from Kluveromyces marxianus IMB3, Bioprocess Eng.
Pigments 56 (2003) 239–249. 19 (1998) 427–430.
[20] Y.-S. Ho, W.-T. Chiu, C.-C. Wang, Regression analysis for the sorption [35] F. Kargi, S. Ozmihci, Comparison of adsorption performances of pow-
isotherms of basic dyes on sugarcane dust, Bioresource Technol. 96 dered activated sludge and powdered activated carbon for removal of
(2005) 1285–1291. turquoise blue dyestuff, Process Biochem. 40 (2005) 2539–2544.