Proceedings of the 11th International Conference on Environmental Science and Technology

Chania, Crete, Greece, 3 – 5 September 2009

DETERMINATION OF THE OPTIMUM COAGULANT DOSE (ALUMINUM

SULPHATE) IN THE WATER TREATMENT PLANT OF ATHENS IN GALATSI

S. BAIRAMIDIS1, P.A. PARASKEVAS1, * and D. KOUBAROU2

1
University of the Aegean, Department of Environmental Studies, University Hill, 81100
Mytilene, Lesvos, Greece.
2
Athens Water Supply and Sewerage Company (EYDAP), Oropou Str. Galatsi, Athens
10141, Greece
*e-mail: ppar@env.aegean.gr

ABSTRACT

The present work took place in the water treatment plant of Athens (Athens Water Supply
and Sewerage Company) in Galatsi in order to study of effectiveness of various doses of
the coagulant, sulphurous aluminum 43% at volume, with addition of 0.1 ppm
polyelectrolyte for the treatment of untreated water of low turbidity (3-4 NTU) which is
observed mainly during the summer months, when also this study took place.
For this aim, comparative laboratorial experiments of coagulation (jar-tests) took place
from water that had been taken from the reservoir of untreated water and parameters
such as the absorption in the 254 nm for the estimation of turbidity and the residual
concentration of aluminum of treated water were measured. From the data of turbidity of
the treated water after the settling tanks as well as the turbidity of untreated water the
optimum dose of reaction agent of coagulation was determined. In addition a cross-
correlation study of residual aluminum and turbidity of the treated water was realized.
The study of the more suitable coagulant dose took place in two time periods. In the first
period from 16 until 25 July 2008 the doses of coagulant that were used in Jar - test were
10, 12, 15, 18, 20 and 22 ppm with the more suitable dose located in the range 15-18
ppm. In the second period from 26 July until 25 August 2008 the doses of coagulant used
in Jar - test were 14, 15, 16, 17 and 18 ppm, doses that resulted from the first
measurements. The lower values of turbidity in this case were observed in the range 15 -
17 ppm and exactly for doses 15 and 16 ppm. It must be noticed that for water of higher
turbidity in the region 12-14 NTU, observed mainly during rainy periods, the doses that
were reported were changed to higher concentrations.

KEYWORDS: Turbidity, Jar-test, Coagulant, Sulphurus aluminum, polyelectrolyte, Water

treatment.

1. INTRODUCTION
The sulphurous aluminum has been used a lot of years as coagulant in the treatment of
water (ASCE, 1993; Pontius Fred., 1990). The doses that are used depend on the quality
of untreated water and as a result when the environmental conditions change the quality
of water also changes (Crittenden J. et. al., 2005). The method used for the determination
of the new suitable dose is the method of Jar-test.
Therefore, the aim of this work was the study of effectiveness of various doses of the
coagulant sulphurous aluminum in the treatment of water. For this reason comparative
laboratorial experiments of coagulation (jar-tests) were realized to water that had been
taken from the reservoir of untreated water and the measured parameters include the
absorption in the 254 nm for the estimate of turbidity and the residual concentration of
aluminum.

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2. MATERIALS AND METHODS

2.1 Jar test and calculation of turbidity of the treated water

For the jar test procedure, one stirring appliance with 5 stirrers, 6 glasses of one liter
volume and 2 mechanic precision pipettes were used (Amirthajah A., 1988). In addition
the solution of Al2(SO4)3 57% at weight and 43% at volume and 0.1 ppm of polyelectrolyte
(Magnafloc LT 25) were used for the process of coagulation to be done in the water
samples. The turbidity of the treated water sample was measured by using a turbidity-
meter device.
Water sample was taken from the reservoir of crude water and 800 ml was placed in each
one of the glasses of the jar test appliance. The stirring appliance was regulated in the
250 turns per minute speed and in the first minute using a mechanical precision pipette a
quantity of sulphurous aluminum solution was added in each sample, so that the
concentration of the sulphurous aluminum in 800 ml to be equal with 10, 12, 15, 18, 20
and 22 ppm respectively. In the second minute, in each sample, with the use of a pipette
again, a solution of polyelectrolyte was added, in such quantity that it corresponded to 0.1
ppm for 800 ml of the sample. The samples were still left for one minute to be stirred in
the 250 rpm and then there was a constant stirring in the 30 turns per minute (slow mix)
for 20 minutes, in order the flocculation to be done. After this process and the creation of
floccs the samples were left in calm to achieve the settling of the floccs. During the
second week of measurements, the same experiment took place with new doses 14, 15,
16, 17 and 18 ppm, a choice based on the results from the experiment of the first week.
After the mentioned process from each glass water samples were taken with the 25 ml
glass pipette and placed in a special reception of the turbidity-meter. After 1 minute of the
activation of the appliance the value of the turbidity of the sample was given in NTU.

2.2 Determination of residual aluminum

For the determination of residual aluminum, a fasmatofotometre of ultraviolet-visible, for

use in the 535 nm, with optics way of 1 cm and type A glass was used. Volumetric bottles
were used rinsed initially with HCl 1+1 and afterwards with sufficient quantity of water
(free aluminum) so that all the quantity of acid was removed.
Stock solution of aluminum (Al 1000 mg/l), intermediate model solution of aluminum (AI 10
mg/l), model solution of aluminum of work (AI 1 mg/l), H2SO4 solution 1N, H2SO4 solution
0.02 N, ascorbic acid solution, acetic acid solution 1N, acetic regulation solution, coloring
dense solution and coloring thin solution were needed for the process to be done.
Initially, fresh model solution of aluminum (AI 1 mg/l) was used and the necessary volume
was transferred in volumetric bottles of 50 ml, so a line of model solutions 0-280 mg/l (with
base sample 25 ml) was prepared. In each bottle deionized water was added up to a total
volume roughly 25 ml. Then in every of the volumetric bottles of 50 ml, 1 ml 0.02 N H2SO4
was added and good stirring took place. In addition 1 ml of solution of ascorbic acid was
added and the solution was stirred. Moreover, 10 ml of regulating solution was added and
the mix was stirred again. With the suitable dosimetric pump, 5 ml thin coloring was
added. Finally the solution was supplemented with deionized water. The solution was
stirred well and left for 8 minutes for the growth of color. In the last stage, absorption of
models solutions was measured after transferring samples of them inside the 1 cm
cerumen which was entered in a special reception of fasmatofotometre. The absorption
was calculated in 535 nm and then it was annihilated with the blind sample. The
concentrations of model solutions AI (1 mg/l) with the corresponding absorptions that were
measured were placed in diagram in order to make the calibration curve.
The following process was followed in the laboratory samples too. Initially 25 ml of sample
was transferred in volumetric bottle of 50 ml and 4 ml of H2SO4 0.02N were added. Next 1

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ml of ascorbic acid solution was added in the bottle and was stirred. Then, 10 ml of
regulating solution were added and the solution was stirred again. With the suitable
dosimetric pump, 5 ml of thin coloring solution was added, and the volumetric bottle was
supplemented with deionized water. Finally, the solution was stirred well and was left for 8
minutes for the growth of color. Then the solution was transferred in 1 cm cerumen and its
absorption was measured in the 535 nm, after the annihilation of the body with the use of
blind sample. By the calibration curve and the recorded absorption, the residual aluminum
of each sample was determined in ppb (μg Al/l).

3. RESULTS AND DISCUSSION

3.1 Turbidity results

All the measurements which took place during the period 16/7 - 25/7/08 are shown in
Table 1 and are presented in graphical form in Fig. 1a. The optimum coagulant dose was
observed in the range 15-18 ppm for almost all the samples while the turbidity appears to
increase with higher doses.

Table 1. Results for the parameter of turbidity (NTU) (16/7-25/7/08)

10 12 15 18 20 22 Untreated
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) water
16 July 0.281 0.131 0.146 0.148 0.234 0.223 1.15
17 July 0.207 0.257 0.181 0.396 0.224 0.313 1.2
18 July 0.279 0.142 0.192 0.18 0.235 0.279 1.08
21 July 0.271 0.243 0.116 0.164 0.194 0.343 1.2
23 July 0.45 0.279 0.183 0.179 0.245 0.423 0.88
24 July 0.378 0.292 0.179 0.184 0.198 0.274 1.18
25 July 0.423 0.227 0.189 0.182 0.227 0.442 1.13
This fact is also confirmed by the following diagram (Figure 1b) where the average
turbidity observed for each concentration separately is shown. It is also obvious that the
lowest concentrations were observed in the range 15 – 18 ppm with the 15 ppm dose to
present a better output.

Figure 1. a) Fluctuation of turbidity for all measurements (from 16/7-25/7/08)

b) Average turbidity concentrations for every dose (16/7-25/7/08)

It should be mentioned that the turbidity values observed for 18 ppm coagulant dose
presented a high standard deviation from average value (0.085324) (Table 5), a fact that
however is due to a relatively extreme value observed at the rurbidity measurement of
July 17th (0.396 NTU). If this value is excluded, (outlier) the average value of turbidities
observed after the treatment is 0.173 NTU that is to say little higher than the 15 ppm and

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the standard deviation from the average value is equal to 0.0141, value exceptionally
small.
Estimating the mentioned results during 28/7-25/8/08, different doses of coagulant were
selected to be used. The new doses used in each sample respectively, were 14, 15, 16,
17 and 18 ppm of aluminum shulphate 43% per weight. Generally satisfactory results
were found in doses between 14-17 ppm (Table 2).

Table 2. Results for the parameter of turbidity (NTU) (28/7-25/8/08)

14 15 16 17 18
(ppm) (ppm) (ppm) (ppm) (ppm)
28 July 0.172 0.226 0.291 0.304 0.323
29 July 0.359 0.212 0.226 0.336 0.521
31 July 0.897 0.332 0.436 0.589 0.509
5Aug. 0.422 0.252 0.227 0.375 0.457
6 Aug 0.236 0.255 0.218 0.236 0.317
7 Aug 0.318 0.29 0.287 0.216 0.321
12 Aug 0.348 0.293 0.263 0.256 0.211
14 Aug 0.463 0.577 0.454 0.612 0.625
19 Aug 0.344 0.404 0.347 0.314 0.392
20 Aug 0.398 0.314 0.219 0.253 0.312
25 Aug 0.328 0.3 0.292 0.283 0.324

The results above are also confirmed by the graphical form of Figure 2a where it appears
that the average values of turbidity are smallest for doses of the 16 and 15 ppm
respectively, while the results for the 17 ppm dose are also satisfactory. The standard
deviation for these three medium values is respectively 0.102 for the 15 ppm, 0.084 for
the dose of 16 ppm and 0.135 and for the 17 ppm dose (Table 5).
Moreover, from the Fig. 2b, it appears that for most of the measurements the lowest
turbidities were observed for the 16 ppm dose, while the samples with dose of the
coagulant 15 ppm was the next more efficient coagulation dose.

Figure 2. a) Average turbidity concentrations for every dose (26/7-25/8). b) Fluctuation of

turbidity, on doses of sulphurous aluminum 15 16 and 17 ppm during 28/7-25/8
It should be noticed however that the aforementioned doses correspond to untreated
water of about 3 – 4 NTU turbidity. When, on July 18th, the sample water was taken from
the output of the filters just after backwash cleaning with turbidity 12 – 14 NTU, higher
dose of coagulant was required.

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3.2 Residual Aluminum results

During the period 16/7-25/7/08, in the case of residual aluminum, the results were not as
evident as in the case of turbidity parameter. From the following Table 3 and Fig. 3a that
present the average values fluctuation of residual aluminum in treated water, it appears
that in the range 15 - 18 ppm the concentration of residual aluminum in treated water had
also the lowest values.

Table 3. Results for the parameter of residual aluminum (ppb) (16/7-25/7)

10 12 15 18 20 22
(ppm) (ppm) (ppm) (ppm) (ppm) (ppm)
16July 278.14 315.36 298.2 307.67 309.49 307.33
17July 294.03 297.74 277.28 251.03 251.72 243.94
18July 348.3 217.1 228.3 230 314.6 318.5
21July 457.93 301.98 202.1 192.22 212.68 239.02

23July 346.1 215.2 324.3 221.8 265.2 379.3

24July 253.1 187.3 198.35 156.81 165.36 170.89
25July 452.3 324.7 192.3 287.3 254.2 342.1

In the second period of measurements between 26/7-25/8  (Table  4  and  Fig.  3b),  similar
results concerning the lowest values for both the parameter of turbidity and the residual
aluminum were found. The lowest values for residual aluminum concentration happened
in the range 15-17 ppm and the lowest value was given for the 16 ppm dose.

Table 4. Results for the parameter of residual aluminum (ppb) (28/7-25/8/08)

14 15 16 17 18
(ppm) (ppm) (ppm) (ppm) (ppm)
28 July 364.14 378.43 434.11 352.66 355.46
29 July 399.85 380.65 360.67 378.14 393.77
31 July 357.19 318.3 311.84 334.8 332.1
5Aug. 434.5 326.12 279.02 234.05 262.81
6 Aug 397.34 330.56 314.06 293.21 304.4
7 Aug 415.97 331.72 312.7 298.61 277
12 Aug 398.5 330.2 332.5 340.9 298.2
14 Aug 212.5 228.3 209.5 312.8 400.5
19 Aug 400.5 308.5 243.2 202.1 280.5
20 Aug 319.5 302.3 297.6 218.3 346.7
25 Aug 342.3 243.4 213.5 300.1 343.8

3.3 Cross-correlation of Residual aluminum – turbidity

From the following Table 6 it appears clearly that during the period 16/7-25/7 the cross-
correlation of residual aluminum and turbidity of treated water was positive and in most of
the cases very good.

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Figure 3. a) Fluctuation of average values of residual aluminum observed after the
treatment of samples with coagulant doses during 16/7-25/7 b) Fluctuation of average
values of residual aluminum observed after the treatment of samples with coagulant
doses during 28/7-25/8. 

Table 5. Average values of turbidity and residual aluminum for each dose used
     1st period     
Turbidity Residual
Coagulant average aluminium
dose values Standard average values Standard
(ppm) (ΝΤU) deviation (ppb) deviation
10 0.311 0.0874 344.587 85.027
12 0.224 0.0639 265.626 56.787
15 0.169 0.028 245.833 152.617
18 0.207 0.0853 235.261 52.306
20 0.222 0.0192 253.321 52.35
22 0.309 0.069 285.854 73.349
nd
2 period
14 0.39 0.187 367.481 61.569
15 0.314 0.102 316.226 49.496
16 0.296 0.084 300.791 65.238
17 0.343 0.135 301.861 51.569
18 0.392 0.122 329.113 30.475

This fact was expected since the reduction of residual aluminum is connected with the
coagulation and settling that takes place which also leads to the reduction of turbidity of
treated water.
The fact that in certain cases the correlation of these parameters was small and negative
is due to mistakes of the laboratorial activity that possibly happened during the time from
the end of jar test till the measurement of the samples. This results to the resuspension of
some floccs so the turbidity values do not agree with the values of the residual aluminum.
 

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Table 6.  Cross-correlation of residual aluminum of - turbidity during period16/7-25/7

and 28/7-25/8/08
Correlation Correlation
factor factor
between between
Turbidity- Turbidity-
residual residual
Date aluminum Date aluminum
28/7/2008 0.14 16/7/2008 -0.6
29/7/2008 0.67 17/7/2008 -0.55
31/7/2008 0.94 18/7/2008 0.94
5/8/2008 0.35 21/7/2008 0.47
6/8/2008 -0.25 23/7/2008 0.89
7/8/2008 0.69 24/7/2008 0.724
12/8/2008 0.72 25/7/2008 0.89
Average 0.4
14/8/2008 0.87 value
19/8/2008 0.31
20/8/2008 0.53
25/8/2008 0.7
Average 0.533
value

4. CONCLUSIONS 
 
For untreated water of low turbidity (3-4 NTU) that is observed mainly the summer
months, when the present research took place, the optimum coagulant dose of sulphurous
aluminum, in laboratory conditions, is found in the range between 15-16 ppm, with the
dose of the 16 ppm to present slightly better results regarding the size and the uniformity
of the floccs, and consequently the treated water turbidity.
However, if the untreated water has high turbidity concentrations, that is to say between
12-14 NTU or even higher values that can be observed during winter months, although
the results were judged satisfactory for the mentioned doses, most probably the optimum
output was achieved with higher sulphurous aluminum concentration.
The measurement of residual aluminum concentration in the treated water showed lowest
values in the region between 15-18 ppm, fact that is also confirmed by the correlation
between concentration of residual aluminum and turbidity of treated water, which had
positive and in most of the cases very good values. This fact was expected since the
reduction of residual aluminum is connected with the coagulation and sedimentation that
takes place which also leads to the reduction of turbidity in the treated water.

REFERENCES
1. Amirthajah A. (1988) ‘Design of Flocculation Systems in Water Treatment Plant Design’,
edited by R.L Sanks, Ann Arbor Science.
2. ASCE, AWWA, (1993), ‘Water Treatment Plant Design’, 2nd ed., NY.
3. Crittenden et. al. (2005) ‘Water Treatment, Principles & Design’, MWH, 2nd ed., J. Wiley &
Sons.
4. Pontius F. (ed.) (1990) ‘Water Quality and Treatment’, AWWA, 4th ed., Mc Graw Hill.

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