A statistical experiment design approach for arsenic removal by coagulation process

using aluminum sulfate
Meltem Bilici Baskan
a,
⁎, Aysegul Pala
b
a
Pamukkale University, Department of Environmental Engineering, 20070 Kinikli, Denizli, Turkey
b
Dokuz Eylul University, Department of Environmental Engineering, 35160 Buca, Izmir, Turkey
a b s t r a c t a r t i c l e i n f o
Article history:
Received 12 October 2009
Received in revised form 11 December 2009
Accepted 16 December 2009
Available online 13 January 2010
Keywords:
Arsenic removal
Aluminum sulfate
Coagulation
Box–Behnken design
Residual aluminum
Organic polymers
Arsenic removal from drinking water by precipitation–coprecipitation method using aluminum sulfate was
investigated. The Box–Behnken statistical experiment design (BBD) and response surface methodology
(RSM) were used to investigate the effects of major operating variables. Initial arsenate concentration, pH,
and aluminum sulfate dose were selected as independent variables in BBD while arsenate removal was
considered as the response function. The predicted values of arsenate removal obtained using the response
function were in good agreement with the experimental data. Aluminum sulfate was found as effective and
reliable coagulant due to required dose, residual arsenate and aluminum concentration. The optimum pH
range for maximum arsenate removal was 6–8. In the low initial arsenate concentrations, the highest
arsenate removal efficiency was obtained at high aluminum sulfate doses, while in the high initial arsenate
concentrations, the highest arsenate removal efficiency was provided at low coagulant doses. This study
showed that statistical design methodology was an efficient and feasible approach in determining the
optimum conditions for arsenic removal by coagulation and flocculation. The use of all types of coagulant
aids increased the removal efficiency of the treatment method but application of cationic polyelectrolyte was
more effective than anionic and nonionic ones.
© 2009 Elsevier B.V. All rights reserved.
1. Introduction
Arsenic is a naturally occurring element in the earth's crust, and is
found throughout the environment [1]. The elevated concentrations
of arsenic in the environment occur from both natural and
anthropogenic sources [2]. Millions of people are at serious risk of
arsenic poisoning in many countries around the world, especially in
West Bengal, India, and Bangladesh due to their exposure to high
arsenic drinking water sources [3–6]. Arsenic exposure via drinking
water can cause various types of skin lesions, skin and other cancers,
cardiovascular, respiratory, and neurological disorders [7–14]. The U.
S. Environmental Protection Agency (EPA) decreased the maximum
contaminant level (MCL) of arsenic in drinking water from 50 μg L
−1
to 10 μg L
−1
in 2006 due to fatal toxicity of arsenic on human health
[15]. Natural water sources contained much higher levels of arsenic
(20–3000 μg L
−1
) than MCL were determined in western Turkey. The
natural enrichment of arsenic in groundwaters is related to the borate
deposits, and the arsenic complexes present in soils [16–20].
Arsenic can occur in the environment in several oxidation states but
in natural waters it is mostly found in inorganic form as oxyanions of
trivalent arsenite [As(III)] or pentavalent arsenate [As(V)]. Organic
arsenic forms may be produced by biological activity, mostly in surface
waters, but they are rarely quantitatively important [21]. The specia-
tions of arsenic are dependent on the type and amounts of sorbents, pH,
redox potential, and microbial activity [22]. The predominant As(III)
compound is neutral in charge, while the As(V) species are negatively
charged in the pH range of 4–10 [23,24]. Therefore As(III) is less
efficiently removed than As(V) from aqueous solutions by almost all of
the arsenic removal technologies and preoxidation of As(III) to As(V)
using some oxidizing chemical agents like chlorine and potassium
permanganate is necessary for better removal [6].
Various technologies are available for the removal of arsenic from
contaminated water including chemical precipitation or coagulation,
adsorption, lime softening, ion exchange, and membrane separation
[4,25–30]. The mentioned methods are mainly effective for arsenate
removal. Coagulation can effectively remove arsenic from water
besides many suspended and dissolved constituents, notably turbid-
ity, color, phosphate, and fluoride [31–33]. Commonly used chemicals
in this technique are aluminum salts such as aluminum sulfate and
ferric salts such as ferric chloride or ferric sulfate because of theirs low
cost and relative ease of handling. In arsenic removal by this process,
chemicals transform dissolved arsenic into an insoluble solid which is
precipitated. Dissolved arsenic may also be adsorbed on the solid
hydroxide surface site and be coprecipitated with other precipitating
species [6]. The solids can be removed through sedimentation and/or
filtration.
Desalination 254 (2010) 42–48
⁎ Corresponding author. Tel.: +90 258 2963332; fax: +90 258 2963262.
E-mail address: mbilici@pau.edu.tr (M. Bilici Baskan).
0011-9164/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2009.12.016
Contents lists available at ScienceDirect
Desalination
j our nal homepage: www. el sevi er. com/ l ocat e/ desal
Organic polymers are used as coagulant aid for water and waste-
water treatment [34]. Flocculation is the action of polymers to form
bridges between the larger mass particles or flocs and to bind the
particles into large agglomerates or clumps [35]. Several studies have
been reported for arsenic removal from water by coagulation using
ferric or aluminum salts [1,4,28,32,33,36–41]. However, there are
limited numbers of studies investigating the effects of cationic
[4,28,39,42] and anionic [28] polymers for increasing of arsenic
removal. No studies exist on the use of nonionic polymers as coag-
ulant aid for arsenic removal by coagulation in the literature.
Usually coagulation process is enhanced by adjusting pH and
electrolyte concentration to reduce the absolute values of zeta
potentials of particles, and by optimizing coagulation kinetics [33].
In the present study, the BBD method was selected to optimize major
operating variables of the coagulation process. The BBD is a RSM used
for analysis the experimental design data [43]. The RSMis essentially a
particular set of mathematical and statistical methods for designing
experiments, building models, evaluating the effects of variables, and
searching optimum conditions of variables to predict targeted re-
sponses. The RSM does not require a large number of runs and also
does not require too many levels of the independent variables [44,45].
The major objective of this study is to investigate removal
efficiencies of arsenate from tap water by precipitation/coprecipita-
tion with aluminum sulfate as a coagulant. The BBD method was used
to investigate the effects of important operating parameters such as
initial arsenic concentrations, pH, and coagulant doses on percent
removal of arsenic and to find the most suitable combination of
variables resulting in maximum arsenic removal efficiency. The re-
gression model provided an excellent explanation of the relationship
among the independent variables and the response. The effect of
aluminum sulfate dose on the residual aluminum after treatment was
also investigated. Furthermore the effects of small amount of organic
polymers as coagulant aid were determined. Cationic, anionic, and
nonionic types of polyelectrolytes and different dosages of themwere
tested for maximum arsenate removal. The findings provided new
insight into the availability of BBDfor arsenate removal by coagulation
process and better understanding of the organic polymers effect on
arsenate removal efficiency.
2. Materials and methods
2.1. Materials
The chemical composition and some properties of the tap water
used in this study are listed in Table 1. Sodiumarsenate (Na
2
HAsO
4
.7-
H
2
O) was used to provide stock arsenate solution (purchased from
Sigma). In the experimental studies, working solutions were freshly
prepared from the stock arsenic solution for each experimental run.
Analytical reagent grade chemicals were used for the preparation of
all solutions. Stock solutions of aluminum sulfate (Al
2
(SO
4
)
3
.18H
2
O)
were prepared with deionised water. Magnafloc LT22, Magnafloc
LT27, and Magnafloc LT20 were used as cationic, anionic, and nonionic
polyelectrolytes, respectively. Hydrochloric acid (1 M, 0.1 M) and
sodium hydroxide (1 M, 0.1 M) solutions were prepared for pH
adjustment.
2.2. Experimental procedure
The coagulant was added to each 1 L of sample water containing
various concentrations of As(V). Prior to addition of coagulant, the
sample water pH was adjusted by adding HCl or NaOH solution. A
series of jar test experiments were performed at 120±2 rpm for
3 min. After the rapid mixing, 30 min of slow mixing at 45±2 rpm
was provided. Then, the jars were allowed to settle for 30 min. At the
end of the settling period, water samples were taken from the
supernatants, filtered by 0.45-μm pore size membrane filter, and
stored for analysis by HCl addition to conserve the samples until the
arsenic was detected. In the second series of the experiments, cationic,
anionic, and nonionic polyelectrolytes were added in conjunction
with aluminum sulfate to sample water in order to determine the
organic polymers effect on arsenate removal. The coagulation
conditions were carried out in the same way as mentioned above.
All the experiments were performed in duplicate to evaluate test
reproducibility under identical conditions and the arithmetic average
result of the two experiments was reported in this study.
2.3. Analytical methods
Arsenic in the influent and effluent aqueous solutions was mea-
sured by the hydride generation procedure coupled with ICP-atomic
emission spectrometry (HG-ICP-AES) (Optima 2100 DV). Hydride
generation involves the production of volatile hydrides upon a
chemical treatment with a strong reducing agent, typically sodium
borohydride (NaBH
4
). The sodium borohydride instantaneously con-
verts As(III) to arsine gas at roomtemperature, while the reduction of
As(V) to arsine occurs relatively slow. Therefore, a total arsenic
determination requires a prereductant such as KI to convert As(V) to
As(III) prior to the arsine formation step [46,47]. In this study, the
sample water (20 mL) was first mixed with 6 mL HCl (10%) and 2 mL
of reducing agent (5% KI and 5% ascorbic acid), and then allowed to
react for 30 min at dark place to reduce As(V) to As(III). Finally, 10 mL
solution was taken for the analysis of As(III) concentrations. The
determination of aluminum concentrations was also made by the use
the HG-ICP-AES. Each analysis of arsenic and aluminum concentra-
tions was duplicated. The arithmetic average of the two analyses
results was reported in this study.
2.4. BBD and data analysis
The RSM was used to investigate the influence of major operating
variables on arsenic removal efficiency and to find the most suitable
combination of variables resulting in maximum arsenic removal ef-
ficiency. The BBD with three factors and three levels, including five
replicates at the centre point for estimation of errors, was used to
evaluate the main and interaction effects of the factors and to fit a
second-order model with quadratic terms.
For precipitation/coprecipitation process, three important operat-
ing parameters such as initial arsenic concentration, coagulant dose,
and pH were considered as the independent variables, while arsenic
removal efficiency was the response (Y) (dependent variable). Initial
arsenic concentration (X
1
) was varied between 10 and 1000 µg L
−1
,
while coagulant dose (X
2
) was ranged from 0.5 to 80 mg L
−1
, and pH
(X
3
) was ranged from 4 to 9. The low, middle, and high levels of each
variable were designated as −1, 0, and +1, respectively. The coded
and actual values of the three independent variables together with the
response for BBD are shown in Table 2. An empirical second-order
Table 1
Characterization of the tap water used for experiment.
Components Concentration
pH 7.9
Turbidity, NTU 0.1
Chloride, mg L
−1
44
Nitrate, mg L
−1
4
Iron, mg L
−1
0.040
Aluminum, mg L
−1
0.012
Manganese, mg L
−1
0.001
Sodium, mg L
−1
22.8
Conductivity, µS cm
−1
462
Sulfate, mg L
−1
38
43 M. Bilici Baskan, A. Pala / Desalination 254 (2010) 42–48
polynomial model (Y) (response function) for predicting the optimal
point was in the following form:
Y = b
0
+ ∑
k
i =1
b
i
X
i
+ ∑
k
i =1
b
ii
X
2
i
+ ∑
k−1
i =1

k
j =i + 1
b
ij
X
i
X
j
ð1Þ
where Y is the predicted response (percent As(V) removal), b
0
is the
offset term and b
i
is the linear effect while b
ii
and b
ij
are the square
and interaction effects, respectively. X
i
and X
j
are the coded values of
independent variables and k is the number of the independent
variables. The software Design Expert (Version 7.0.0, Stat-Ease Inc.,
Minneapolis, USA) and Statistica 5.0 were used for the experimental
design, determination of the coefficients, the data analysis, and the
graph plotting. The validity of the model and the reliability of the
statistical experimental strategies were determined by comparing the
experimental and predicted values. Furthermore, the predicted
arsenic removal efficiencies from response function were experimen-
tally verified in an additional study.
3. Results and discussion
3.1. Optimization of parameters for As(V) removal
The removal of As(V) from drinking water was investigated by
precipitation/coprecipitation method using aluminum sulfate as a
coagulant. The effects of process variables such as initial arsenic
concentration, coagulant dose, and pH on the arsenic removal
efficiency were investigated using RSM according to BBD. Different
response functions such as linear, interactive, quadratic and cubic
models were used to correlate the experimental data and to obtain the
regression equation. To decide about the adequacy of the models to
represent arsenate removal by aluminum sulfate, three different tests
namely sequential model sum of squares, lack of fit tests, and model
summary statistics were carried out in the present study and the
results are presented in Table 3. Cubic model was not recommended
for this system due to insufficient points to estimate the coefficients
for this type of the model. Sequential model sumof squares and model
summary statistics indicated that the quadratic model provided the
best fit to experimental data with the lowest standard deviation, the
highest correlation coefficient, adjusted R
2
, predicted R
2
values, and
the lowest p value. Therefore, the quadratic model was chosen for
further analysis.
Experimental data were used for determining of the response
function (Eq. (1)) coefficients for each independent variable. The
response function with the determined coefficients for percent
arsenate removal (Y) is presented by Eq. (2).
Y =−172:377 + 64:209 × 10
−3
X
1
+ 1:513X
2
+ 54:251X
3
−71
× 10
−6
X
1
X
2
+ 14:340 × 10
−4
X
1
X
3
+ 14:644 × 10
−2
X
2
X
3
−5:850 × 10
−5
X
2
1
−1:910 × 10
−2
X
2
2
−4:113X
2
3
:
ð2Þ
The predicted values of percent As(V) removal were determined
by the response function with the obtained coefficients. The
experimental results and the predicted values of percentage arsenate
removal using aluminum sulfate are presented in Table 2. The high
value of regression coefficient (R
2
=0.9726) indicates that the model
predictions fit satisfactorily with the experimental observations.
The statistical significance of the response function was checked
by F-test, and the ANOVA results for response surface quadratic model
and model terms are summarized in Table 4. The model F value and
Table 2
The BBD with coded/actual values for the three independent variables and the
comparison of observed and predicted As(V) removal efficiency.
Experiment
no.
Actual and coded levels of variables As(V) removal
efficiency (%)
Initial As(V)
concentration (X
1
)
Coagulant
dose (X
2
)
pH (X
3
) Observed Predicted
1 1 (1000) 0 (40.25) −1 (4.0) 37.30 40.83
2 −1 (10) 1 (80.00) 0 (6.5) 90.00 82.08
3 0 (505) 0 (40.25) 0 (6.5) 95.25 95.49
4 1 (1000) 0 (40.25) 1 (9.0) 84.40 81.40
5 0 (505) 0 (40.25) 0 (6.5) 95.45 95.49
6 0 (505) 0 (40.25) 0 (6.5) 95.64 95.49
7 0 (505) 0 (40.25) 0 (6.5) 94.65 95.49
8 1 (1000) −1 (0.50) 0 (6.5) 14.70 22.62
9 0 (505) −1 (0.50) 1 (9.0) 13.07 8.15
10 −1 (10) 0 (40.25) 1 (9.0) 70.00 66.47
11 0 (505) 0 (40.25) 0 (6.5) 96.44 95.49
12 −1 (10) −1 (0.50) 0 (6.5) 0.00 8.45
13 0 (505) −1 (0.50) −1 (4.0) 11.68 0.23
14 −1 (10) 0 (40.25) −1 (4.0) 30.00 33.00
15 0 (505) 1 (80.00) 1 (9.0) 96.63 100.00
16 0 (505) 1 (80.00) −1 (4.0) 37.03 41.95
17 1 (1000) 1 (80.00) 0 (6.5) 99.10 90.65
Table 3
Adequacy of the model tested for arsenate removal.
Source Sum of squares df Mean square F pNF Remark
Sequential model sum of squares
Mean 66261.33 1 66261.33 – – –
Linear 13033.18 3 4344.39 5.79 0.0097 –
2FI 867.54 3 289.18 0.33 0.8073 –
Quadratic 8271.32 3 2757.11 30.95 0.0002 Suggested
Cubic 621.89 3 207.30 490.72 b0.0001 Not recommended
Residual 1.69 4 0.42 – – –
Total 89056.95 17 5238.64 – – –
Lack of fit tests
Linear 9760.75 9 1084.53 2567.35 b0.0001 –
2FI 8893.20 6 1482.20 3508.75 b0.0001 –
Quadratic 621.89 3 207.30 490.72 b0.0001 Suggested
Cubic 0.00 0 – – – Not recommended
Pure error 1.69 4 0.42 – – –
Source Model summary statistics
Std. dev. R
2
Adjusted R
2
Predicted R
2
Press Remark
Linear 27.40 0.5717 0.4729 0.3347 15165.48 –
2FI 29.82 0.6098 0.3757 −0.0438 23793.09 –
Quadratic 9.44 0.9726 0.9375 0.5634 9952.80 Suggested
Cubic 0.65 0.9999 0.9997 – – Not recommended
44 M. Bilici Baskan, A. Pala / Desalination 254 (2010) 42–48
very low probability value (0.0001) indicated that the model was
statistically significant and model equation can adequately be used to
describe the arsenate removal under a wide range of operating
conditions. The p values are used to estimate whether F is large
enough to indicate statistical significance and used to check the
significance of each coefficient. p values lower than 0.05 indicate that
the model and model terms are statistically significant [48]. In this
case, the model equation and all regression coefficients are significant
except for one linear coefficient (X
1
) and two cross-product coef-
ficients (X
1
X
2
and X
1
X
3
). Although they are nonsignificant, they are
still considered in Eq. (2) because it is a hierarchical model. Fur-
thermore the study of contour plots and the regression equation
highlight certain interactions between the selected parameters as
well as their individual effects on arsenate removal. The analysis
showed that the form of the model chosen to explain the relationship
between the factors and the response is correct and can be used to
navigate the design space.
The high value of R
2
(0.9726) indicated a high dependence and
correlation between the observed and the predicted values of response.
The value of adjusted R
2
(0.9375) suggested that the total variation of
about 94% for arsenate removal was attributed to the independent
variables and only about 6%of the total variationcannot be explained by
the model. The value of the adequate precision is a measure of the signal
(response) to noise (deviation) ratio. A ratio greater than 4 is desirable.
In the present study, the ratio was found to be 14.899, which indicates
the adequate signal. Therefore the quadratic model can be used for the
arsenate removal by coagulation process.
Variations of percent arsenate removals with the initial arsenate
concentration at different pH and constant aluminum sulfate
concentration of 40 mg L
−1
are depicted in Fig. 1. pH value was
prominently effective for arsenate removal efficiency. As it can be
seen in Fig. 1, percent arsenate removal increased with increasing pH
and the optimum pH range for arsenate removal by coagulation was
6–8. In the high acidic pH, the arsenate removal efficiency declined
sharply. Similarly, high alkaline pH above 8 caused lower efficiencies.
The obtained optimum pH range fromthis study is in good agreement
with the values given in the literature [28,38]. The effect of the pH
range on the arsenate removal efficiency is related to the solubility of
the amorphous hydroxide solid of aluminum. Arsenate removal ef-
ficiency increased in the pH range of 6 to 8 because of the fact that the
amorphous hydroxide solid is stable in this pH range.
According to the results of the BBD method for aluminum sulfate,
arsenate removal was highly pH-dependent and the optimum pH
range was 6–8. Fig. 2 shows the variations of percent arsenate re-
movals with initial arsenate concentrations at different Al
2
(SO
4
)
3
concentrations and constant pH of 7. Aluminum sulfate concentration
is important in determining the level of arsenic removal as shown in
figure. When aluminum sulfate is added to arsenic contaminated
water, aluminum sulfate dissociates and forms aluminum hydroxide,
which coprecipitates with arsenic. The possible chemical equations of
aluminum sulfate coagulation are as follows [49,50]:
Al
2
ðSO
4
Þ
3
:18H
2
O→2Al
þ3
þ 3SO
2−
4
þ 18H
2
O Aluminum sulfate dissolution
2Al

þ 6H
2
O→2AlðOHÞ
3
þ 6H
þ
Aluminum precipitation
H
2
AsO

4
þ AlðOHÞ
3
→Al–As complex Coprecipitation
During coagulation, arsenic is removed through three main mech-
anisms including precipitation, coprecipitation, and adsorption. The
formation of the insoluble compounds Al(AsO
4
) is seen in first step. In
coprecipitation, the soluble arsenic species are incorporated into a
growing metal hydroxide phase via inclusion, occlusion, or adsorp-
tion. Finally, the soluble arsenic is binded electrostatically to the
external surfaces of the insoluble metal hydroxide. All three of these
mechanisms can independently contribute towards arsenic removal.
Table 4
ANOVA results of the second-order polynomial equation for percentage arsenate
removal using aluminum sulfate.
Source Sum of squares df Mean square F value p value
Model 22172.04 9 2463.56 27.65 0.0001

X
1
258.78 1 258.78 2.90 0.1321
X
2
10033.07 1 10033.07 112.63 b0.0001

X
3
2741.33 1 2741.33 30.77 0.0009

X
1
X
2
7.84 1 7.84 0.088 0.7753
X
1
X
3
12.60 1 12.60 0.14 0.7180
X
2
X
3
847.10 1 847.10 9.51 0.0177

X
1
2
867.86 1 867.86 9.74 0.0168

X
2
2
3834.89 1 3834.89 43.05 0.0003

X
3
2
2781.93 1 2781.93 31.23 0.0008

Residual 623.57 7 89.08
Lack of fit 621.89 3 207.30
Pure error 1.69 4 0.42
Corrected total 22795.62 16
R
2
=0.9726, adjusted R
2
=0.9375, R=0.9862; adequate precision=14.899 (N4).
⁎ Significant variable.
Fig. 1. Contour plot of the combined effects of initial arsenate concentration and pH on
arsenate removal efficiency at a constant aluminum sulfate dosage of 40 mg L
−1
.
Fig. 2. Contour plot of the combined effects of initial arsenate concentration and
aluminum sulfate dose on arsenate removal efficiency at a constant pH of 7.
45 M. Bilici Baskan, A. Pala / Desalination 254 (2010) 42–48
Because of the Al(AsO
4
) solid could not be easily formed in arsenic
contaminated drinking water source, precipitation may not contrib-
ute significantly towards the overall performance. However, copre-
cipitation and adsorption are both active arsenic removal mechanisms
[1,31,51,52].
It was found in this study that the addition of coagulant caused
a substantial increase in arsenate removal because the addition of
coagulants facilitates the removal of arsenate from the aqueous
stream by converting the soluble As(V) species into insoluble pro-
ducts. When the aluminum sulfate dose is increased, more aluminum
oxide is formed. It caused a greater surface area for arsenate ad-
sorption and a lower residual arsenic concentration [4]. But above a
certain aluminum sulfate dose, the increase in arsenate removal was
not significant. Coagulant dose above 50 mg L
−1
slightly increased the
percent arsenate removal. In the initial arsenate concentration of
10 μg L
−1
, the highest arsenate removal efficiency, about 91%, was
obtained at coagulant dose of 66 mg L
−1
, while in the initial arsenate
concentrations of 500 and 1000 μg L
−1
, the highest arsenate removal
efficiency, 100%, was provided at coagulant doses 42 and 56 mg L
−1
,
respectively. The natural water containing a low quantity of colloids
requires high concentrations of coagulant to achieve the destabiliza-
tion of colloidal matters due to difficulties in collision between the
colloids. However in the high quantity of colloids, the highest removal
efficiency achieves at low coagulant dose. Therefore in the present
study, for high initial arsenate concentration, the highest arsenate
removal efficiency was provided at low coagulant dose because of the
higher collision probabilities of the colloids.
The obtained results are consistent with the previous observations
on arsenate removal fromdrinking water using aluminumsulfate. The
results of the previous studies on coagulation with aluminum and
ferric salts for arsenate removal showed that ferric salts are more
effective than aluminum salts on a weight basis [1,28,32,36,38,53].
This difference may be attributed to incomplete precipitation of added
aluminum as the amorphous hydroxide solid because iron is more
soluble than aluminum in water [28,36,52]. The obtained results from
the present study and our previous study about the arsenate removal
by ferric salts [53] showed that Fe(III) ions were more effective and
economic than Fe(II) ion, and aluminum sulfate was more effective
than Fe(II) ion due to required lower coagulant dose and pH.
Furthermore iron salts were effective in a wider pH range than
aluminum sulfate. The use of an iron based coagulants was
advantageous above pH 7.5 because of its lower solubility under
basic conditions. However optimum pH range for aluminum sulfate
was found as 6–8 in the present study. In conclusion, excellent arsenic
removal was possible with both Fe(III) ions and aluminumsulfate, and
residual arsenic concentration was reduced to less than 10 µg L
−1
.
In natural waters, as aforementioned, arsenic predominantly
occurs in the trivalent [As(III)] and pentavalent [As(V)] form. As(III)
is much more toxic, soluble, and mobile than As(V), so its removal
efficiency is much lower than that of As(V) when conventional arsenic
removal technologies are used [54,55]. Therefore in this study As(V)
removal fromdrinking water was investigated. However the ability of
the proposed system to achieve the maximum acceptable concentra-
tion for arsenic in drinking water is dependent on the concentration of
As(III) in the source water. When As(III) is present in a significant
amount, As(III) oxidation is a precondition before the proposed
system is applied because As(III) has very little affinity for aluminum
hydroxides.
3.2. Model validation and confirmation
In order to determine the accuracy of the predicted model, three
experiments different from BBD points were carried out. In one of
them, the aforementioned optimum coagulant dose and pH at the
initial arsenate concentration of 500 μg L
−1
were used. The experi-
mental and predicted values were compared in Table 5. Validation
experiments confirmed the suitability and the accuracy of the model.
The predicted values were in close agreement with the experimental
values. Therefore, BBD was a reliable and effective method in de-
termining the optimum conditions for arsenate removal by coagula-
tion. This study also provided useful information and reference
conditions with respect to optimization of other chemical processes
using BBD.
3.3. Arsenic removal efficiency considering variations in residual
aluminum
The aluminum sulfate dose has a striking influence on arsenic
removal. However residual aluminum concentration after sedimen-
tation and filtration in the effluent must be taken into consideration
because of the health effects of aluminum. The previous studies on
health effects of aluminum in drinking water showed that high
consumption of aluminum from drinking water may be a risk factor
for Alzheimer's disease and a relationship exists between the number
of diagnosed Alzheimer's disease cases and the level of aluminum
present in the drinking water [56,57]. The amount of aluminum
present in drinking water has been recommended to be below
200 μg L
−1
by the World Health Organization. The obtained results
fromthis study showed that in the lowinitial arsenate concentrations,
the highest arsenate removal efficiency required a high aluminum
sulfate dose. Therefore residual concentration of aluminum at the low
initial arsenate concentration was monitored for determination the
failure of the coagulation process. The effect of aluminum sulfate
dosage on the arsenic removal efficiency and the relationship
between coagulant dose and residual aluminum for initial arsenate
concentration of 50 μg L
−1
are shown in Fig. 3. Although it has been
supposed that overdose of aluminum sulfate may result in high
residual aluminum [32,58], relatively higher residual aluminum was
found in underdose range as shown in Fig. 3. Residual aluminum
concentration was affected by residual arsenic concentration as well
as coagulant dosage. Above a certain aluminum sulfate dosage
(50 mg L
−1
), the increase in arsenate removal was not significant.
In the coagulant dose above 50 mg L
−1
, residual arsenate concentra-
tion slightly decreased but residual aluminum increased. Kang et al.
[32] also noted that the highest soluble residual aluminum was found
in the underdose aluminum-based coagulant range in sample water
Table 5
Comparison of the experimental and predicted values for different Box–Behnken
experimental design points.
As(V) concentration
(μg L
−1
)
Al
2
(SO
4
)
3
concentration
(mg L
−1
)
pH Efficiency (%)
Observed Predicted
50 50 7 85 88
500 42 7 99 100
100 30 8 65 69
Fig. 3. Effects of aluminum sulfate dosage on the residual aluminum and arsenate
removal efficiency.
46 M. Bilici Baskan, A. Pala / Desalination 254 (2010) 42–48
containing low turbidity. Because the maximum contaminant level of
aluminum in drinking water is 200 μg L
−1
, aluminum sulfate was
found as an effective and reliable coagulant due to required
concentration and residual aluminum.
3.4. Effects of organic polymers
Organic polymers assist in the joining and enmeshing of the
particles together. The use of organic polymers supplies to increase the
size, strength and settleability of the flocs [59]. In viewof this, cationic,
anionic, and nonionic polyelectrolytes were tried to investigate the
effect on removal efficiencies of arsenate from tap water by
precipitation–coprecipitation with aluminum sulfate. The impacts of
polyelectrolyte types and amounts for the initial arsenate concentra-
tion of 50 μg L
−1
were determined. Fig. 4 depicts the variations of
percent arsenate removal at a constant Al
2
(SO
4
)
3
concentration of
40 mg L
−1
by enhancedcoagulationwithcationic, anionic, or nonionic
polyelectrolyte ranging within 0.35 to 3.5 mg L
−1
.
Fig. 4 indicates that there is no appreciable increase in arsenate
removal in case of using nonionic polyelectrolyte. Arsenate concen-
tration was not decreased to below 10 μg L
−1
using anionic and
nonionic polyelectrolytes. Application of cationic polyelectrolyte was
more effective than anionic and nonionic ones. This can be attributed
to the fact that these polymers increase the cationic character of the
inorganic coagulant, resulting in the formation of solids, which are
more likely to adsorb oxyanions (arsenic) [28,60]. The use of cationic
polyelectrolyte dose of 2 mg L
−1
together with aluminum sulfate
dose of 40 mg L
−1
provided arsenate removal of 81% and residual
arsenate concentration was reduced to below 10 μg L
−1
while using
aluminum sulfate concentration of 40 mg L
−1
without addition of
polymer caused 76% arsenate removal. The results of previous studies
about the organic polymers effects on arsenic removal also indicated
that the addition of cationic polymer as a coagulant aid has an effect
on the residual arsenic concentration [4,28,39]. Zouboulis and
Katsiyoannis [28] showed that cationic polyelectrolytes are more
effective than anionic ones. No studies exist on the use of nonionic
polymers as coagulant aid for arsenic removal by coagulation in the
literature.
4. Conclusions
The precipitation/coprecipitation method by aluminum sulfate as
a coagulant and cationic, anionic, or nonionic polyelectrolyte as
coagulant aids was used for arsenate removal from tap water. The
RSM and the BBD were used to determine the effects of major
operating variables on the arsenate removal efficiency, to achieve
statistically reliable results for arsenate removal by coagulation and
flocculation, and also to determine the optimal conditions for
maximizing the removal. The obtained results suggested that
statistical design methodology offers an efficient and feasible
approach for arsenate removal and it could be employed to determine
the optimum conditions for arsenate removal while minimizing the
number of experiments required.
The experimental studies demonstrated that the aluminumsulfate
is an effective and reliable coagulant considering the required
concentration and residual arsenate, aluminum concentration after
sedimentation and filtration in the effluent. The optimum pH range
for arsenate removal by coagulation using aluminum sulfate was 6–8.
At the constant pH of 7, percent arsenate removal increased with
addition of coagulant due to chemical destabilization of colloidal
particles by neutralizing the charges that keeps them apart. It was
found that the arsenate concentration can be reduced down to less
than 10 μg L
−1
in the initial arsenate concentration ranging from10 to
1000 μg L
−1
. In the initial arsenate concentration of 10 μg L
−1
, the
highest arsenate removal efficiency, about 91%, was obtained at
coagulant dose of 66 mg L
−1
, while in the initial arsenate concentra-
tions of 500 and 1000 μg L
−1
, the highest arsenate removal efficiency,
100%, was provided at coagulant doses 42 and 56 mg L
−1
, respec-
tively. The application of polyelectrolytes resulted in the formation of
greater particles, faster floc formation, and produce denser and
stronger flocs [42,61]. Although all types of polymers increased the
removal efficiency of the treatment method, application of cationic
polyelectrolyte was more effective than anionic and nonionic ones.
Acknowledgements
This study was supported by the Izmir Environmental Protection
Foundation and Scientific Research Projects of the Dokuz Eylul
University, Izmir, Turkey under grant number of 2005.KB.FEN.003.
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