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Sulphate control by ettringite precipitation in textile

industry wastewaters
a a a
Işık Kabdaşlı , Azra Bilgin & Olcay Tünay
a
Environmental Engineering Department, Civil Engineering Faculty, İstanbul Technical
University, Ayazağa Campus, 34469 İstanbul, Turkey
Accepted author version posted online: 02 Apr 2015.Published online: 16 Apr 2015.

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To cite this article: Işık Kabdaşlı, Azra Bilgin & Olcay Tünay (2015): Sulphate control by ettringite precipitation in textile
industry wastewaters, Environmental Technology, DOI: 10.1080/09593330.2015.1026245

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 Environmental Technology, 2015
http://dx.doi.org/10.1080/09593330.2015.1026245

Sulphate control by ettringite precipitation in textile industry wastewaters

Işık Kabdaşlı ∗ , Azra Bilgin and Olcay Tünay
Environmental Engineering Department, Civil Engineering Faculty, İstanbul Technical University, Ayazağa Campus, 34469 İstanbul,
Turkey
(Received 30 January 2015; accepted 2 March 2015 )

In the present study, ettringite precipitation was theoretically and experimentally evaluated as a means of sulphate removal.
The results showed that ettringite precipitation is an effective and reliable method for sulphate removal. Synthetically pre-
pared samples which were simulated to total wastewaters originating from the textile industry (sulphate concentration of 0.06
M) and to dye bath effluent (sulphate concentration of 0.22 M) were subjected to ettringite precipitation using the systems
with Na2 SO4 –AlCl3 –Ca(OH)2 –NaOH, Na2 SO4 –AlCl3 –Ca(OH)2 , and Na2 CO3 –Na2 SO4 –AlCl3 –Na(OH)2 . An equilibrium
model involving precipitation more than one solid phase and with ionic strength correction was used to predict the sulphate
removal efficiency as well as solution composition. The optimum pH for ettringite precipitation in all systems was found to
Downloaded by [New York University] at 09:47 09 June 2015

be around 12.0. By the application of the method, 0.06 M initial sulphate concentration was reduced down to 60 mg/L for
synthetically prepared samples and 325 mg/L for real wastewater. For the concentrated samples of 0.22 M initial sulphate,
remaining sulphate levels varying between 230 and 280 mg/L were obtained for both synthetic and real wastewater samples.
Keywords: ettringite; modelling; precipitation; sulphate removal; textile industry wastewater

1. Introduction
Sulphate is an important parameter in wastewaters in
terms of its impact on sewer systems and on some treat-
ment applications and receiving media. It is a regulated
parameter in pretreatment standards and in some of the
direct discharge standards. Some industries, particularly
agro-industries such as textile and fermentation, discharge
considerable amounts of sulphate into the environment.
Sulphate treatment can be realized by either membrane
processes or chemical precipitation. The characteristics
of industrial wastewaters frequently pose problems in the
application of membrane processes. These processes are
also costly unless they serve materials or water reuse.
Chemical precipitation is based on formation of sulphate
salts of low solubility. Calcium and barium are the two
most common agents employed for sulphate precipitation.
Sulphate precipitation as calcium sulphate is advantageous
in many aspects such as cost, ease of application and sludge
removal. The main drawbacks of the process are the high
solubility of calcium sulphate and existence of interfer-
ing ions in the wastewaters. Barium sulphate precipitation
is very efficient; however, its application is rather rare
due to its limitations such as cost and toxicity of barium
salts. Ettringite (Ca6 Al2 O6 ·3CaSO4 ·32H2 O) is a sulphate
salt having lower solubility than that of calcium sulphate
and has the potential of being used as a means of sul-
phate control. This subject has been treated in the literature
widely in the area of concrete corrosion [1–4] but very lim-
ited information exists with regard to sulphate treatment
and control.[5–7] Pehlivanoğlu et al. [8] theoretically stud-
ied the ettringite precipitation and the formation of other
solid phases. In their study, effluent sulphate concentra-
tions, which could be obtained by the process, were also
evaluated. Bilgin [5] evaluated the ettringite precipitation
both theoretically and experimentally using textile indus-
try effluents. Recently, ettringite precipitation was applied
to indigo dyeing effluent to remove sulphate and provided
up to 99.5% removal efficiency.[7]
This paper aims to analyse ettringite precipitation on
both theoretical and experimental bases and to assess its
potential to be used as a method of sulphate removal from
wastewaters. Experimental studies were conducted on both
real textile wastewaters and synthetically prepared sam-
ples simulating textile industry wastewaters. Wastewater
samples were taken as high sulphate containing dye bath
samples and relatively low sulphate containing combined
wastewaters.
2. Materials and methods
2.1. Selection of the systems
Ettringite precipitation involves the addition of more than
one chemical and often results in the precipitation of
more than one solid phase depending on the solution

*Corresponding author. Email: kabdasli@itu.edu.tr

© 2015 Taylor & Francis

 2 I. Kabdaşlı et al.
composition and operating conditions. Therefore, selection
of the systems was realized to account for all potential
cases to define the conditions that may be encountered
in the applications. One of the factors having importance
is the initial sulphate concentration. The sulphate control
for pretreatment has been generally practiced as the sul-
phate level in the wastewater is above CaSO4 solubility,
namely higher than 2000 mg/L. On the other hand, one
of the typical and the most frequently encountered sul-
phate problems is textile industry effluents. The sulphate
problem in this industry can be evaluated on the basis of
sources. While total wastewaters may contain several thou-
sand mg/L sulphate, some process sources such as dye bath
effluents may bear tens of thousands mg/L sulphate. Some
other industrial wastewaters such as fermentation may also
exhibit similar sulphate profiles. Therefore, textile indus-
try total wastewaters and dye bath effluents were taken as
the bases for the definition of the systems to be considered
Downloaded by [New York University] at 09:47 09 June 2015
in the present study. Evaluation of the literature [9,10] and
a textile plant from which the wastewater samples were
provided for characterization yielded following sulphate
levels; the total textile wastewater sulphate concentration
of 0.06 M (5760 mg SO4 /L) and the dye bath effluent sul-
phate concentration of 0.22 M (21,400 mg SO4 /L). These
figures were taken as the bases for the definition follow-
ing systems. On the other hand, carbonate or bicarbonate
content of wastewater is of importance due to the inter-
ference with ettringite precipitation via calcium carbonate
(CaCO3 ) precipitation. Finally, chemical doses and pH
ranges were selected to delineate the other solid phases
precipitated together with ettringite and their effects on
sulphate removal.
2.2. Experimental study
The experimental study was planned to compare with and
verify the theoretical model results and to make an appli-
cation on real wastewater samples. Synthetic samples were
prepared to represent the model conditions. Two textile
wastewater samples were used; one was from a dye bath,
the other was from the total effluent. The characterization
of these samples is given in Table 1. The ionic strength
of the dye bath sample was also high enough for the
assessment of the effect of ionic strength.
Synthetic samples were also prepared to simulate
wastewater samples for the evaluation of the effect of the
wastewater matrix on the precipitation efficiency. They
Table 1. Characterization of samples.
Parameter Unit Total wastewater Dye bath
Sulphate mg/L 2450 21,400
Alkalinity mg CaCO3 /L 2280 8900
Sodium mg/L 3400 13,000
pH – 9.99 10.55
were prepared using deionized water with a conductivity
of 0.055 μS/cm. The deionized water was produced using
Sartorius Arium 611-UV Water Purification System. As
soon as produced, the deionized water was boiled to purge
CO2 to obtain CO2 -free water and stored in an airtight
bottle for one day before using.
2.3. Experimental procedure
All precipitation experiments were conducted in 500 mL
Erlenmeyer flasks with the stopper to ensure the closed
system conditions. Homogeneous mixing conditions were
provided with a magnetic stirrer. Chemical addition and pH
adjustment were made under flash-mixing conditions. And
then, the solutions were mixed using magnetic stirrers at a
constant speed of 300 rpm at least one week to ensure equi-
librium conditions. After reaching equilibrium, the sam-
ples were passed through membrane filters for the measure-
ment of sulphate, calcium, and pH. Na2 SO4 and Na2 CO3
were used as sulphate and carbonate sources in the prepa-
ration of the synthetic samples. Ca(OH)2 and AlCl3 ·6H2 O
were used as calcium and aluminum sources in all exper-
iments. Unless otherwise stated, calcium and aluminium
were used at stoichiometric to sulphate (Ca/Al/SO4 :6/3/2).
In the case of carbonate containing samples, calcium dose
was increased as the equivalent to CaCO3 (Ca/CO3 :1/1).
pH was adjusted using either Ca(OH)2 or NaOH. pH was
measured with the Orion 720 model pH meter. All analyses
were made in accordance with Standard Methods.[11] All
reagents used in this work were analytical grade.
3. Theoretical treatment
3.1. The methodology and definition of the systems
The purpose of the theoretical treatment was to explore and
evaluate the ettringite precipitation. It is a complex system
involving a number of variables and parameters affecting
the precipitation efficiency. The methodology employed
for the solution was definition of the systems under consid-
eration and then to obtain solutions of these systems under
assumed conditions. The solutions were realized by first
defining the species existing in the heterogeneous system
of precipitation including the species that were formed as
solid phases. Then, the solution to the system was obtained
by defining the equations (through equilibrium conditions,
mass balances and charge balance) whose number equal to
the number of species involved and assuming the equilib-
rium was set. The pH was selected as the master variable
for all the systems defined. Selection of the systems was
aimed to evaluate the system behaviour as well as to serve
establishing the operating conditions for the application of
ettringite precipitation for sulphate removal and control. As
defined in Materials and Methods, each system was defined
to assess the effect of an important variable or condition
on the precipitation efficiency, namely the final sulphate
 Environmental Technology 3

Table 2. Equilibrium constants.[13,14]

Species log K

Ca3 Al2 O6 ·3CaSO4 ·32H2 O (s)a Ksp = [Ca2+ ]6 × [SO2− − 12 − 111.3

4 ] × [Al ] × [OH ]
3 3+ 12

− 2 − 4
Ca3 Al2 O6 CaSO4 ·18H2 O (s)b Ks = [Ca2+ ]4 × [SO2−
4 ] × [Al(OH)4 ] × [OH ] − 29.43
CaCO3 (s) Ks = [Ca2+ ] × [CO2− 3 ] − 8.35
Al(OH)3 (s) Ksp = [Al ] × [OH− ]3
3+ − 33.5
H2 CO∗3 Ka,1 = [H2 CO∗3 ] / [HCO− 3 ] × [H ]
+ − 6.42
HCO−3 Ka,2 = [HCO− 2−
3 ] / [CO3 ] × [H ]
+ − 10.305
CaOH+ β1 = [CaOH+ ] / [Ca2+ ] × [OH− ] 1.305
CaSOo4 β1 = [CaSOo4 ] / [Ca2+ ] × [SO2− 4 ] 2.31
CaCOo3 β1 = [CaCO3 ] / [Ca ] × [CO2−
o 2+
3 ] 3.2
CaHCO+3 β1 = [CaHCO3 ] / [Ca ] × [HCO−
+ 2+
3] 1.26
AlOH2+ β1 = [AlOH ]/ [Al ] × [OH ]
2+ 3+ − 9.0
Al(OH)+ β2 = [Al(OH)+ − 2
Downloaded by [New York University] at 09:47 09 June 2015

2 ] / [Al ] × [OH ]
3+ 18.7
2
Al(OH)o3 β3 = [Al(OH)o3 ] / [Al3+ ] × [OH− ]3 27.0
Al(OH)−4 β4 = [Al(OH)− 4 ] / [Al ] × [OH ]
3+ − 4 33.0
+
AlSO4 β1 = [AlSO+ 4 ] / [Al ] × [SO4 ]
3+ 2−
1.9
Al(SO4 )−
2 β2 = [Al(SO4 )− 2 ] / [Al ] × [SO4 ]
3+ 2− 2
3.2
−
NaSO4 β1 = [NaSOo4 ] / [Na+ ] × [SO2− 4 ] 0.72
a Ettringite.
b Monosulphate.

concentration in solution. Among the considered variables the system are Ca2+ , Al3+ , Cl− , Na+ , OH− , H+ , SO2−
4 ,
were ionic strength, complex formation, carbonate content, NaSO− o + − o
4 , CaSO4 , CaOH , Al(OH)4 , Al(OH)3 , Al(OH)2 ,
+
+ −
precipitation of more than one solid phases. Molar concen- AlOH , AlSO4 , Al(SO4 )2 , and solid phase or phases.
2+

trations were used in the equilibrium equations for all theo-

retical solutions except for the case evaluating the effect of
ionic strength where activities were accounted for. Activity
coefficients were calculated using the method of Millero
and Schreiber.[12] The equilibrium constants used in the
theoretical solutions were for temperature of 25°C, 1 atmo-
sphere pressure and zero-corrected ionic strength. These
constants are given in Table 2. The systems considered for
the theoretical solutions are explained as follows.
3.1.1. Na2 SO4 –AlCl3 –Ca(OH)2 –NaOH system
In this system (System A), the addition of calcium, alu-
minium, and sulphate was in the stoichiometric ratios
of ettringite and pH adjustment was made with NaOH.
The initial sulphate concentration was selected as 0.06
M. Since the ions remaining in the solution, particularly
sodium added in high concentrations for raising the pH to
elevated levels, reached high concentrations, this system
was mainly used to assess the effect of ionic strength on the
process efficiency. On the other hand, increasing sodium
ion concentration resulted in the formation of NaSO− 4 concentration of 890 mg/L and sulphate concentration of
which increased the sulphate solubility. The species in
3.1.2. Na2 SO4 –AlCl3 –Ca(OH)2 system
In this system (System B), Ca(OH)2 was used for both pre-
cipitation of ettringite and pH adjustment. This requires the
addition of excess calcium over stoichiometric to ettringite
and reflects the effect of common ion on the solubil-
ity of ettringite. This system also indicates the effect of
the CaSOo4 complex on the solubility as its concentration
increases. The initial sulphate concentration was selected
as 0.06 M. The species involved in this system are the same
that of the Na2 SO4 –AlCl3 –Ca(OH)2 –NaOH system.
3.1.3. Na2 CO3 –Na2 SO4 –AlCl3 –Ca(OH)2 –NaOH system
This system was solved for two cases. The first solution
(System C) was made for a concentrated sulphate solu-
tion. The initial sulphate concentration of this system was
high and 0.22 M being equivalent to the textile dye bath
effluent. The total carbonate concentration was 3240 mg/L.
The second (System D) was a solution for total carbonate
2450 mg SO4 /L representing the total textile wastewaters.
 4 I. Kabdaşlı et al.

The systems were aimed to indicate the performance of
the process in both concentrated and diluted solutions.
Since the system was selected to reflect a real case, car-
bonate was also added to the solutions. The effect of
carbonate was through the formation of carbonate com-
plexes as well as precipitation of CaCO3 . The species
involved in the system are Ca2+ , Al3+ , Cl− , Na+ , OH− ,
− −
H+ , SO2− o +
4 , NaSO4 , CaSO4 , CaOH , Al(OH)4 , Al(OH)3 ,
o
Al(OH)2 , AlOH , AlSO4 , Al(SO4 )2 , H2 CO3 , HCO−
+ 2+ + − ∗
3 complex at pH 12.0.
+
CO2−3 , CaCO o
3 , CaHCO 3 and solid phases.
Although in all systems the ettringite was the solid
phase and CaCO3 , together with the ettringite was another
in one case, there were other solid phases precipitat-
ing depending on the dosage of chemicals and pH such
as monosulphate (Ca3 Al2 O6 CaSO4 ·18H2 O) and Al(OH)3 .
These solid phases were accounted for the cases which they
precipitated. These will be emphasized and discussed as
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30 mg/L for the system without correction. This indicated
that the difference between with and without ionic strength
correction in total sulphate concentration in the pH range
of 12.0–13.0 was around 30 mg/L. The solutions could be
made depending on the case and required precision; how-
ever, the difference for these systems seems to be relatively
small. In the ionic strength-corrected system, over 20% of
total sulphate in the solutions was in the form of NaSO− 4
Figure 1(b) depicts the results of the theoretical model
solutions to System B. In this system, ettringite and
Al(OH)3 solids precipitated together below pH 11.55.
Ca(OH)2 began to precipitate as pH reached to 12.3 and
precipitated together with ettringite. Monosulphate precip-
itated with ettringite beginning pH 12.75. Although the
final total sulphate concentrations were very low within
a wide range, around pH 12.0 where Ca(OH)2 did not
precipitate and lime dosing to reach this pH remained

the theoretical solution results are presented.

at a reasonable level seems to represent an optimum.
Beginning pH 12.0, the results of the systems with and
3.2. The theoretical model solutions without ionic strength correction were very close to one
Figure 1(a) displays the theoretical solution results of Sys- another, and total sulphate concentration at pH 12 was
tem A. In this system, Al(OH)3 precipitates up to pH 11.5. around 10 mg/L. The species distribution indicated that
Ettringite was the only solid phase between pH 11.5 and in the ionic strength-corrected system the contributions to
12.0. Ca(OH)2 began to precipitate near pH 12.0 and co- NaSO− o
4 and CaSO4 to total sulphate concentration in the
precipitates with ettringite up to pH 13.0. Beginning pH solutions were about 17% and 14%, respectively.
13.0 monosulphate was the only solid phase. Final total The results of the theoretical model solution to Sys-
sulphate concentrations for ionic strength-corrected system tem C are presented in Figure 2(a). This system represents
were around 60 mg/L and this figure dropped to around a highly concentrated textile dye bath with the initial
sulphate concentration reaching 21,400 mg/L. Below pH
11.5, Al(OH)3 and CaCO3 solids precipitated. Between pH
(a) 140
Model (no ionic strength correction)
120 Model (ionic strength corrected)
Synthetic sample (a) 480 Model (no ionic strength correction)
Sulphate (mg/L)

100 Model (ionic strength corrected)

430 Synthetic sample
380 Dye Bath
Sulphate (mg/L)

80
330
60
280
40 230
20 180
130
0 80
10.5 11 11.5 12 12.5 13 13.5 14
30
pH 11 11.5 12 12.5 13 13.5 14
pH
(b) 180
Model (no ionic strength correction) (b) 500 Model (no ionic strength correction)
160 Model (ionic strength corrected) 450 Model (ionic strength corrected)
140 Synthetic sample 400 Synthetic sample
Sulphate (mg/L)

Total wastewater
Sulphate (mg/L)

120 350
100 300
250
80
200
60 150
40 100
20 50
0 0
11 11.5 12 12.5 13 13.5 14 11 11.5 12 12.5 13 13.5 14
pH pH

Figure 1. Theoretical model solutions and experimental results Figure 2. Theoretical model solutions and experimental results
for (a) System A and (b) System B. for (a) System C and (b) System D.
 Environmental Technology
11.5 and 12.0, Al(OH)3 , CaCO3 and ettringite were the
solids precipitated. Between pH 12.0 and 12.91 ettringite
and CaCO3 and above pH 12.9 ettringite, monosulphate
and CaCO3 phases precipitated together. The optimum pH
range for System C was between 12.0 and 12.5 where only
ettringite and CaCO3 precipitated. For pH 12.0, final total
sulphate concentrations were at the level of 115 and 45
mg/L for ionic strength-corrected and -uncorrected sys-
tems, respectively. The species distribution at pH 12 for
ionic strength-corrected system indicated that a significant
fraction of total soluble sulphate was in the form of NaSO−4
(42%) while the CaSOo4 complex was only about 1.6% of
the total soluble sulphate.
Figure 2(b) displays the results of the theoretical model
solutions to System D. The pH range where only ettrin-
gite and CaCO3 solids precipitated was 12.0–12.5. Total
sulphate concentrations for ionic strength-corrected and -
uncorrected systems were approximately 70 and 40 mg/L,
Downloaded by [New York University] at 09:47 09 June 2015
respectively, at pH 12.0.
4. Evaluation of experimental study results
The experimental study results obtained are shown on
the related figures for the systems. For System A, the
experimental results obtained around pH 12 approximate
the theoretical model results obtained with and with-
out ionic strength correction. However, as pH 13.0 is
approached where monosulphate precipitation began to
dominate experimental, results tend to get closer to ionic
strength-corrected solution line. At any rate, the experi-
mental results are mostly between the bands of theoretical
lines with and without ionic strength correction. The dif-
ferences between the experimental results and theoretically
determined values originate from the accuracy of solutions,
which mainly depend on the selected values of equilibrium
constants as well as from the experimental errors, how-
ever they are assumed to be in an acceptable range. For
System B, three experimental results in the range of pH
12.0–12.65 are quiet consistent with one another and paral-
lel to the theoretical lines, but they are above the theoretical
predictions. The differences are, however, around 20 mg/L.
System C is the most complex one in terms of high dis-
solved solids content and a number of solids precipitating
and dissolving depending on pH. Ettringite theoretically
begins to precipitate at pH 11.5 together with two other
solid phases Al(OH)3 and CaCO3 . The experimental study
was conducted for both real and synthetic wastewaters;
one was the real wastewaters (dye bath effluent and total
wastewater) being taken from a textile plant, the others
were synthetically prepared to simulate the real wastewa-
ters. As seen in Figure 2(a), the experimental results for
textile dye bath effluent at pH 11.6 was 103 mg/L sul-
phate which was close to155 mg/L obtained for the ionic
strength-corrected theoretical model solution. At pH 12.2,
the experimental results for dye bath effluent was 279
mg/L sulphate, which again was very close to the ionic
5
strength-corrected theoretical model value of 296 mg/L.
For the synthetic dye bath sample at a pH of 11.6, the
measured value was 42 mg/L sulphate which was lower
than the theoretical solution and approximated surprisingly
to 72 mg/L which was the result of the theoretical model
solution without ionic strength correction. At pH 12.2, the
experimental result was 205 mg/L, which could be con-
sidered close enough both the theoretical model value of
296 mg/L for the ionic strength-corrected system and to
279 mg/L obtained for the actual sample experiment at
pH 12.2. For System D, which was the actual sample of
total textile wastewaters with 2450 mg/L sulphate concen-
tration, the experimental results were 430 mg/L for pH
11.6 and 272 mg/L for pH 12.62. These values were well
above the ionic strength-corrected theoretical model val-
ues calculated as 91 and 52 mg/L for pH 11.56 and 12.62,
respectively. On the other hand, the experimental results
obtained for the synthetic sample to simulate the total
textile wastewater were 63, 150, and 166 mg/L sulphate
for pH values of 11.79, 12.18, and 12.59, respectively.
The ionic strength-corrected theoretical model value cor-
responding to these pH values were 73, 59, and 51 mg/L.
These indicated that while at pH 11.79 the experimental
result was close to the theoretical model solution, above
this pH, experimental results tended to be higher than the
theoretical model solution values with a difference around
100 mg/L.
5. Conclusions
Several conclusions can be drawn from the results of the
present study. First of all the ettringite precipitation proved
to be a reliable and efficient treatment method for sulphate
removal. It can be used as a viable alternative to barium
sulphate precipitation. The method was also found to be
successful for the indigo wastewater treatment which had
a very complex wastewater matrix.[7] In the present appli-
cation, the method yielded consistent results for a wide
array of conditions. The theoretical models used worked
well. Experimental results were close enough to those pre-
dicted by the model. Ionic strength correction, although
increases the precision of the model, due to low solubility
of ettringite, up to ionic strength of 0.13 M, the modelling
without ionic strength correction which is much easier to
work out provided acceptable approximations. However,
for the high ionic strength system (I = 0.55 M) the dif-
ference between the results with and without correction
has become significant. The examination of the model
results in terms of the distribution of complex species and
final sulphate concentrations indicated that use of sodium
hydroxide or lime for pH adjustment did not result in an
appreciable difference in terms of the process efficiency.
Nor the existence of carbonate, which is an important com-
mon ion, exerted an effect to prevent the use of the process
or limiting the achievable efficiencies. At any case for a
feasible process application, the amount of solids to be
 6 I. Kabdaşlı et al.
produced should be accounted for. The high pH, generally
around 12, applied for the ettringite precipitation requires
a neutralization step before discharge. This application is
also necessary to control aluminium concentrations which
may be up to 70 mg/L remaining in the solution after ettrin-
gite precipitation. Ettringite precipitation can directly be
applied to high sulphate containing wastewater or as a pol-
ishing method following CaSO4 precipitation. The latter
depending on the case may provide advantages in terms of
cost, ease of operation and reuse potential of precipitated
CaSO4 .
Disclosure statement
No potential conflict of interest was reported by the authors.
References
[1] Odler I, Colán-Subauste J. Investigations on cement expan-
Downloaded by [New York University] at 09:47 09 June 2015
sion associated with ettringite formation. Cement Concrete
Res. 1999;29:731–735.
[2] Evjua C, Hansen S. The kinetics of ettringite formation
and dilatation in a blended cement with β-hemihydrate
and anhydrite as calcium sulfate. Cement Concrete Res.
2005;35:2310–2321.
[3] Chrysochoou M, Dermatas D. Evaluation of ettringite and
hydrocalumite formation for heavy metal immobilization:
literature review and experimental study. J Hazard Mater.
2006;136:20–33.
[4] Rajasekaran G. Sulphate attack and ettringite formation in
the lime and cement stabilized marine clays. Ocean Eng.
2005;32:1133–1159.
[5] Bilgin A. Determination of the factors effecting the
removal of sulfate by the ettringite precipitation. İstanbul:
Environmental Engineering Department, İstanbul Technical
University; 1999. Turkish.
[6] Şimşeker M. Treatment of indigo dyeing textile wastew-
ater by electrocoagulation and other physical–chemical
processes. İstanbul: Graduate School of Science Engineer-
ing and Technology, İstanbul Technical University; 2009.
Turkish.
[7] Tünay O, Şimşeker M, Ölmez-Hancı T, Kabdaşlı I. Sulphate
removal from indigo dyeing wastewaters by ettringite pre-
cipitation. Fresen Environ Bull. 2014;23(12b):3405–3409.
[8] Pehlivanoğlu E, Kabdaşlı I, Tünay O. Sulfate removal by
ettringite precipitation. Fresen Environ Bull. 1998;7:826–
832.
[9] Kabdaşlı NI. The approach and application bases for sul-
fate treatment by chemical precipitation. İstanbul: Institute
of Sciences, İstanbul Technical University; 1995. Turkish.
[10] Kabdaşlı NI, Tünay O. Pretreatment of sulfate containing
industrial wastewaters using calcium salts. Paper presented
at: The Second Specialized Conference on Pretreatment
of Industrial Wastewaters; 1996 October 16–18; Athens,
Greece.
[11] American Public Health Association, American Water
Works Association, Water Environment Federation. Stan-
dard Methods for the Examination of Water and Wastew-
ater. 20th ed. Washington, DC: American Public Health
Association, American Water Works Association, Water
Environment Federation; 1998.
[12] Millero FJ, Schreiber DR. Use of the ion pairing model
to estimate activity coefficients of the ionic components of
natural waters. Am J Sci. 1982;282:1508–1540.
[13] Sillen LG, Martell AE. Stability constants of metal–ion
complexes. Special Publication, Number 17. London: The
Chemical Society; 1964.
[14] Sillen LG, Martell AE. Stability constants of metal–ion
complexes. Special Publication, Number 25. London: The
Chemical Society; 1971.