Journal of Colloid and Interface Science 282 (2005) 314319

www.elsevier.com/locate/jcis

The removal of textile dyes by diatomite earth

Emin Erdem , Glay lgeen, Ramazan Donat
Department of Chemistry, Faculty of Science and Arts, Pamukkale University, Denizli, Turkey
Received 27 May 2004; accepted 18 August 2004
Available online 11 November 2004

Abstract
The adsorption of some textile dyes by diatomite was investigated using Sf Blau BRF (SB), Everzol Brill Red 3BS (EBR), and Int Yellow
5GF (IY). Adsorption of these textile dyes onto diatomite earth samples was studied by batch adsorption techniques at 30 C. The adsorption
behavior of textile dyes on diatomite samples was investigated using a UVvis spectrophotometric technique. The effect of particle size
of diatomite, diatomite concentration, the effect of initial dye concentrations, and shaking time on adsorption was investigated. Adsorption
coverage over the surface of diatomite was studied using two well-known isotherm models: Langmuirs and Freundlichs. These results
suggest that the dye uptake process mediated by diatomite has a potential for large-scale treatment of textile mill discharges. According to
the equilibrium studies, the selectivity sequence can be given as IY > SB > EBR. Values of the removal efficiency of the dyes ranged from
28.60 to 99.23%. These results show that natural diatomite holds great potential to remove textile dyes from wastewater.
2004 Elsevier Inc. All rights reserved.
Keywords: Adsorption; Textile dyes; Diatomite; Clay; Isotherm

1. Introduction
The presence of color in many industrial effluent streams
is aesthetically undesirable. Colored organic effluent is produced in the textile, paper, plastic, leather, food, and mineral processing industries [1]. Water contamination from
dyeing and finishing in the textile industry is a major concern. Discharging large amount of dyes into water resources,
accompanied by organics, bleaches, and salts, can affect
the physical and chemical properties of fresh water. In addition to their unwanted colors, some dyes may degrade
to produce carcinogens and toxic products. Consequently,
their treatment does not depend on biological degradation
alone [2]. Traditionally both biological and chemical methods have been employed for dye removal, but these techniques have not been very successful due to the essentially
nonbiodegradable nature of most dyes.
One of the powerful treatment processes for the removal
of dyes from water at low cost is adsorption. Adsorption
* Corresponding author. Fax: +90-258-2125546.

E-mail address: eerdem@pamukkale.edu.tr (E. Erdem).

0021-9797/$ see front matter 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.08.166

techniques have proven successful in removing colored organics [13]. Several adsorbents are eligible for such a purpose. Activated carbon is the most popular adsorbent and
has been used with great success [4]. However, due to its
difficulty and expense of regeneration, clays are being considered as alternative low-cost adsorbents [35]. A large
number of low-cost adsorbents have been treated for dye
removal. For example, Asfour et al. have studied the adsorption of basic dye Astrazone blue FRR 69 on hardwood
(Beech) sawdust [6]. The use of diatomaceous earth for
the adsorption of methylene blue, Cibacron reactive black
C-NN, and reactive golden yellow MI-2RN has been reported [7]. Dogan and Alkan have investigated the kinetics
of methyl violet adsorption onto perlite [8]. Liversidge et al.
have studied the removal of Basic blue 41 dyes by linseed
cake [9]. Annadurai et al. have studied the adsorption of
various dyes onto cellulose-based wastes [10]. Gupta et al.
have studied the removal of Metomega Chrome Orange GL
by fly ash [11]. The use of acid-activated clay for the removal of basic, acidic, disperse, direct, and reactive dyes has
also been reported. The highest adsorption capacity was observed for basic dyes and the support was proposed as an

E. Erdem et al. / Journal of Colloid and Interface Science 282 (2005) 314319

efficient adsorption medium for their removal from aqueous

solution [12].
Cationic dye molecules also have a very high affinity for
clay surfaces and are readily adsorbed when added to clay
suspensions. Because of their high molar absorptivity, dye
molecules and their aggregates are easily detected by spectrophotometric and photophysical techniques, even at relatively low concentrations [13]. The rigid nature of the dye
clay organic coverage provides a finite surface for adsorption
organic compounds from aqueous solutions. Borisover et al.
found that such dye-based organoclay complexes are effective in reducing aqueous concentrations of nonionic organic
compounds such as atrazine, naphthalene, and phenol [14].
Biosorption is defined as the accumulation and concentration of pollutants from aqueous solutions by the use of
biological materials, thus allowing the recovery and/or environmentally acceptable disposal of the pollutants. Biosorption of various organic pollutants in wastewaters has been
investigated by various workers [1517]. Biosorption for
dyes could be also adopted for the treatment of textile effluents [18,19]. Textile dyes vary greatly in their chemistries,
and their interactions with microorganisms depend on the
chemistry of a particular dye and the specific chemistry of
microbial biomass.
Diatomite is a siliceous rock made up largely from the
skeletons of aquatic plants called diatoms. Apart from being
made of fossil skeletons, diatomite is essentially opaline hydrous silica. It is used as an absorber of hazardous chemicals
in handling and storage and refining various acids [20]. Diatomaceous earthotherwise known as diatomitefound in
abundance in the Middle East has been used in a number of
applications, especially in the removal of heavy metals [21].
It has a unique combination of physical and chemical properties, which make it applicable as a substrate for adsorption
of organic pollutants as a filtration medium in a number of
industrial uses [22]. Its high permeability and high porosity
make it a cheap alternative to activated carbon. It is against
this background that the feasibility of using diatomite for removal of color from textile wastewaters was attempted.
The aim of this study is to produce a satisfactory effluent
for discharge into receiving waters or for reuse as a water
supply from different concentrated textile dye solutions (SB,
EBR, and IY), using diatomite earth samples. The adsorption
properties and adsorption isotherms of natural diatomite for
some textile dyes in solution were investigated.

2. Experimental
2.1. Materials
Three commercial dyes were chosen for this study. SB,
EBR, and IY dyes were provided as gift samples by CEPA
Textile Fabrics (Denizli, Turkey). The molecular structure
diagrams and formulae of SB, EBR, and IY were not provided for commercial reasons. IY represents an indanthrene

315

dye, while EBR and SB are examples of the reactive type,

which is characterized by the presence of nitrogennitrogen
azo bonds.
Diatomite earth was supplied as a natural resource from
the Sarayky basin, Denizli. Sample of 1 kg was washed
several times with deionized water until neutralization of
the decantant was achieved. Finally, the sample was filtered,
dried in an oven at 100 C, sieved, and stored in closed containers for further tests. Major oxide analysis by XRF can
be carried out on as little as 0.5 g of diatomite. The sample material analyzed as a pressed powder was fused into a
glass disk using a suitable flux, such as lithium tetraborate.
Using fused samples produces an evenly dispersed solid solution, which enables a wide range of matrix compositions to
be accurately determined through the normalization of both
particle size and interelement (matrix) effects.
All the chemicals were analytical grades obtained from
Merck.
2.2. Adsorptions
A standard stock solution of the dyes was prepared by
appropriate dilution with deionized water to a final concentration of 1000 mg/L. Dyes were hydrolyzed by Na2 CO3
and Na2 SO4 solutions at the start of the experiment. In the
dyeing of cellulosic fibers with reactive dyes, the addition of
alkali to the dye bath not only promotes formation of a covalent bond between the dye and the cellulosic substitute but
also causes the hydrolysis of the reactive groups in the dye.
Hence, the reactions necessary to introduce the substances
onto the fiber do not run to total completion, and residual reactive hydrolyzed dyes remain in the process water. As a result, the hydrolyzed form of these dyes is found in the textile
factorys discharge wastewater [7]. Thus a study of the hydrolyzed forms of these dyes was carried out. The stock solution was diluted to prepare working solutions. More diluted
solutions were prepared daily as required. The buffer solutions (pH 4, 7, and 9) were used to calibrate the pH meter.
Aqueous solutions of SB was prepared at a final concentration of 1090 mg/L with 10 mg/L intervals. Adsorption isotherm experiments were carried out in 100-ml Erlenmeyer flasks to which 5 g of diatomite (63 m) and 50 ml
of the appropriate concentration of the test dye solution were
added. The samples were subsequently capped and shaken at
125 rpm in a GFL Type 1083 shaker for 3 min at 30 C. After phase separation by centrifugation (2 min at 2000 rpm),
the residual dyes in aqueous solutions were determined using a UVvis spectrophotometer (Shimadzu 1100). The final
dye concentrations were determined using max of each dye.
SB, EBR, and IY textile dyes solutions showed maximum absorbance at wavelengths of 612, 544, and 441 nm.
The concentrations were calculated using the BeerLambert
equation,
absorbance = Cs l,

(1)

where is the molar absorptivity, Cs the concentration of

sample, and l the thickness of the absorbing medium (1 cm).

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E. Erdem et al. / Journal of Colloid and Interface Science 282 (2005) 314319

The amount of adsorbed dye was calculated from the difference between initial and final concentrations.
Adsorption of these textile dyes on natural diatomite was
determined in terms of distribution coefficients, Kd , percentage adsorption, %, or amount sorbed per unit weight of the
sorbent. The percent adsorption and distribution ratio (Kd )
were estimated using the equations [23]
Cj Cf
(2)
100,
Ci
where Ci and Cf are the concentrations of the textile dye in
initial and final solutions, respectively, and
dye removal (%) =

amount of dye in adsorbent V

[ml/g],
(3)
amount of dye in solution
m
where V is the volume of the dye solution (ml) and m is the
weight of the adsorbent (g).
The pH was adjusted to pH 11 by adding sodium carbonate. The flasks were then removed from the shaker and the
final concentration of textile dyes in the solution was measured using the spectrophotometer. Similar procedures were
performed at a solution temperature of 30 C.

Table 1
Chemical composition properties of diatomite earth sample
Constituent

Diatomite (% by weight)

SiO2
Al2 O3
Fe2 O3
CaO
MgO
Na2 O
SO3
LOIa
pH

49.82
1.01
0.67
18.71
1.34
0.15
23.19
4.87
4.85

a Loss on ignition.

Kd =

spectively, by using the equation. Where Ce is the equilibrium concentration in mg/L and Cads shows that the adsorption seems to follow the Freundlich isotherm model as well
as the Langmuir isotherm, where K roughly represents the
adsorption capacity and can be related to the surface energy
as K = RT nbeH/RT and 1/n is the adsorption intensity.
The value of n is usually greater than 1 and must reach some
limit when the surface is fully covered.

2.3. Adsorption isotherm

Equilibrium isotherms are very important in designing
adsorption systems. To estimate the adsorption characteristics of an adsorbent, the adsorption isotherms with a specific adsorbate are carried out. The concentration variation
method is used to calculate the adsorption characteristic of
the adsorbent and the process.
Adsorption coverage over the surface of diatomite was
studied using the two well-known isotherm models: Langmuirs and Freundlichs. The experimental results have been
fitted to the Langmuir model and to the Freundlich model.
The equilibrium data for textile dyes over the concentration range from 10 to 90 mg/L at 30 C has been correlated
with the Langmuir isotherm,
Ce /Cads = 1/Qb + Ce /Q,

(4)

where Ce is the equilibrium concentration textile dyes in solution (M) and Cads is the amount of textile dyes sorbed onto
diatomite, Q and b are Langmuir constants related to sorption capacity and sorption energy, respectively. A linear plot
is obtained when Ce /Cads is plotted against Ce over the entire concentration range of textile dyes investigated
The Freundlich sorption isotherm, one of the most widely
used mathematical descriptions, usually fits the experimental
data over a wide range of concentrations. This isotherm gives
an expression encompassing the surface heterogeneity and
the exponential distribution of active sites and their energies.
The Freundlich adsorption isotherms were also applied for
the removal of textile dyes on diatomite,
log Cads = log K + 1/n log Ce .

(5)

The Freundlich constants of n and K were calculated

from the slope and interception of the Freundlich plots, re-

3. Results and discussion

The chemical composition of diatomite determined by
X-ray fluorescence (XRF) is shown in Table 1. This table shows that the main constituent of diatomite samples is
SiO2 (49.82%). It is not pure hydrous silica but rather contains other associated elements: inorganic matter, principally
calcium, and to a lesser extent ions, metals, alkaline earth
metals, alkali metals, and other minor constituents such as
chlorite and potassium.
3.1. Adsorption of textile dyes
3.1.1. Effect of diatomite concentration
The dependence of SB dye adsorption on diatomite
(300 m) concentration was studied at 30 C by varying the
adsorbent amount from 1 to 9 g while keeping the volume,
50 ml, of the dye solution constant (100 mg/L). The results,
shown in Fig. 1, indicate that the percentage adsorption increases with increasing amount of adsorbent. The increase
in the percentage adsorption with increasing amount of the
sorbent is due to the greater availability of the exchangeable/adsorption sites at higher concentrations of the adsorbent. On the basis of these results 5 g of the diatomite was
used for the further studies.
3.1.2. Effect of particle size of diatomite
Fig. 2 shows the effect of size for a fixed mass of the diatomite particles. It is clear that decreasing the particle size
of diatomite from 300 to 63 m has increased the adsorption
rate of SB. This is because increasing the external surface
area of the diatomite particle exposes more active sites to

E. Erdem et al. / Journal of Colloid and Interface Science 282 (2005) 314319

Fig. 1. Dependence of SB dyes adsorption on diatomite percentage adsorption. (SB conc.: 100 mg/L, particle size of diatomite: 300 m, V : 50 ml,
t: 10 min, T : 30 C.)

Fig. 2. Effect of particle size of diatomite on the adsorption of SB. (SB

conc.: 100 mg/L, m: 5 g, V : 50 ml, t: 10 min, T : 30 C.)

SB molecules. There is a slight effect of particle size of diatomite on adsorption of textile dyes. Therefore, particle size
63 m was found to be appropriate for maximum adsorption
and was used in all subsequent measurements.
3.1.3. The effect of initial dye concentration
As generally expected, a change in the inlet dye concentration of the feed affects the adsorption. The adsorption
of SB was studied as a function of dye concentration. Dye
concentration was varied from 10 to 100 mg/ml. Fig. 3 illustrates the effect of initial dye concentration on adsorption.
Dye adsorption increased in the initial concentration range
from 10 to 100 mg/ml and slightly decreased after 10 mg/ml
for SB.
3.1.4. Effect of shaking time
The effect of shaking contact time was studied using a
constant concentration (10 mg/ml) of dye solution at 30 C.

317

Fig. 3. Variations of adsorption (%) versus initial SB concentration (m: 5 g,

particle size of diatomite: 63 m, V : 50 ml, t: 10 min, T : 30 C).

Fig. 4. Variation in adsorption of SB onto diatomite as a function of shaking time. (SB conc.: 10 mg/L, m: 5 g, particle size of diatomite: 63 m,
V : 50 ml, T : 30 C.)

The adsorption of SB dye onto composite adsorber has been

investigated as a function of time in the range of 130 min.
Fig. 4 shows percentage adsorption with shaking time for
textile dyes. As seen from Fig. 4, a higher removal percentage of textile dyes is obtained at the beginning of the
adsorption. Percent adsorption decreases sharply with increasing shaking time. Quantitative adsorption of dye from
solution was determined within minutes. Therefore, 3 min
shaking time was found to be appropriate for maximum adsorption and was used in all subsequent measurements. It
is interesting to note that percentage adsorption later on decrease with longer periods of shaking. The uptake of dye
by diatomite adsorbent is very rapid; percentage adsorption
reaches a maximum almost immediately after mixing of adsorbent and dye solution.
The adsorption of textile dyes on natural diatomite as a
function of their concentration was studied at 30 C by varying SB and EBR concentrations from 10 to 90 mg/L and IY

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E. Erdem et al. / Journal of Colloid and Interface Science 282 (2005) 314319

Fig. 5. Kd and adsorption of dyes (SB, EBR) by natural diatomite sample as

a function of initial concentration (m: 5 g, particle size of diatomite: 63 m,
m: 5 g, V : 50 ml, t: 3 min, T : 30 C).

Fig. 7. Dye adsorption Langmuir isotherms to diatomite.

Fig. 6. Kd and adsorption of IY dye by natural diatomite sample as a function of initial concentration (m: 5 g, particle size of diatomite: 63 m, m: 5 g,
V : 50 ml, t: 3 min, T : 30 C).

Fig. 8. Langmuir plot for IY dye adsorption onto diatomite.

concentrations from 70 to 630 mg/L while keeping all other

parameters constant. The adsorption and Kd results for dyes
are shown in Figs. 5 and 6. The results show that the percentage color removal of SB, EBR, and IY was decreased when
the initial dye concentration was increased. The Kd values
increase with the decreasing concentration of dyes. In other
words, the Kd values increase as dilution of dye ions in solution proceeds. The affinity of SB, EBR, and IY dyes to diatomite was as follows: IY > SB > EBR. The pH of the dye
is a very important parameter, since it affects the dye adsorption capacity on diatomite. The content of silica in diatomite
gives its structure credibility as a good adsorbent. The silanol
group is a very active group, which can react with many polar organic compounds and various functional groups [7].
Indanthrene dye and unhydrolyzed reactive dyes react with
silanol groups that spread over the surface of diatomite.
3.2. Equilibrium adsorptions isotherms
The pH of the aqueous solution is an important variable
for the adsorption of dyes on the adsorbents. The effect of the

pH on dye adsorption by diatomite was studied at pH 11. The

equilibrium isotherm at 30 C was fitted using a Langmuir
model and compared with the proposed correlation. It appears that Langmuir and Freundlich models were fitted these
data at the solute concentrations in Figs. 79. All constants
obtained by both Langmuir and Freundlich models are listed
in Table 2 with a high correlation coefficient (r 2 > 0.97).
For the Langmuir model, the linearity is well maintained
in the considered concentration range and this indicates that
temperature is the only factor that greatly affects the global
process [24]. It is important to recognize that the mechanism
of dye adsorption on diatomite cannot be determined directly
from the Langmuir or Freundlich fitting. However, from Table 2, it can be concluded that the adsorption isotherms of
SB, EBR, and IY exhibit Langmuir behavior, which indicates monolayer adsorption. The adsorbed dye anions form
a monolayer with sulfonate groups as close as possible to the
adsorbent surface [25].
The n values of SI, EBR, and IY are above 5, indicating that the adsorption of more charged dyes was also more
favorable. Value of n between 2 and 10 show good adsorp-

E. Erdem et al. / Journal of Colloid and Interface Science 282 (2005) 314319

The filtration is an important property of the adsorbents to be

used in water treatment, since most adsorption purification
processes depend on filtration. The filtration process based
on this diatomite represent a possible alternative to the conventional textile dyes separation processes. We can suggest
that plunging process of the packed or pelleted diatomite in
textile wastewater for three min.
Superplasticizers are used to increase the workability of
cement mixes formulated at low water-to cement ratios and
to produce concretes of high strength [28]. Textile dyes have
a superplasticizer effect. Dyed diatomite could be used for
the production of colored and blended cements with a high
strength.
Although real textile effluents contain a mix of more than
one dye, it is essential initially to consider single-dye systems to reduce the complexity of using real textile effluent.
This being said, future work will include studies of multicomponent systems as well as real textile effluent.

Fig. 9. Dye adsorption Freundlich isotherms to diatomite.

Table 2
Isotherm parameters of textile dye adsorption on diatomite sample
Dye sample
SB
EBR
IY

Langmuir parameters

Freundlich parameters

Q (mg/g)

b (l/g)

R2

10.11
5.92
117.75

0.33
1.45
0.10

0.9887
0.9915
0.9770

319

1/n

K (mg/g)

R2

0.18
0.20
0.18

4.12
3.55
3.84

0.9809
0.9878
0.9802

tion [26]. The Freundlich isotherm gives an expression encompassing the surface heterogeneity and the exponential
distribution of active sites and their energies [27]. The numerical value of 1/n < 1 indicates that adsorption capacity
is only slightly suppressed at lower equilibrium concentrations. This isotherms do not predict any saturation of the
sorbent by the sorbate, thus infinite surface coverage is predicted mathematically, indicating multilayer sorption of the
surface. The adsorption of the SB, EBR, and IY was best
represented by the Freundlich model, which indicates heterogeneous surface binding.

4. Conclusion
Diatomite was used as an adsorbent for removal of textile
dyes from water. Diatomite is a locally available, low-cost
adsorbent in Turkey. Diatomite is approximately 500 times
cheaper than commercial activated carbon, CAC. The results
show that SB, EBR, and IY adsorption on diatomite is very
fast compared to that on CAC. Therefore diatomite can be
used as a highly effective low-cost adsorbent for the removal
of indanthrene and reactive dyes.
Crystal structure of diatomite contains some ion-exchangeable cations such as Na+ , Ca2+ , and Mg2+ . These
cations can be exchanged with organic and inorganic cations.
The surface charges of diatomaceous earth may arise from
chemical reactions.
The maximum of recovery dye was obtained at 3 min and
the value rapidly decreased with increasing shaking time.

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