Özdemir, C. ve S., Dursun, “Trihalomethane Determination And Removals From The Main
Discharge Channel Of Konya City (Turkey)”, Environmental Technology, 25(9), 1091 - 1096, 2004.
TRIHALOMETHANE DETERMINATION AND REMOVALS FROM THE MAIN
DISCHARGE CHANNEL OF KONYA CITY (Turkey)
C. OZDEMIR, S. DURSUN
Selcuk University, Engineering & Architecture Faculty, Environmental Eng. Dept,
42031, Konya /Turkey
E-Mail: celozdemir@selcuk.edu.tr
ABSRACT
Konya Main Discharge Channel appears a very important environmental problem due to carrying the domestic waste water of Konya city centre as well as industrial waste water.
Lowest flow rate of the channel was observed in October about 2 10
4
m
3 d
-1
. In this period, channel water is not only waste water but includes more rain water coming from Gölyazı region. Discharge channel water can only reach to Tuz Lake for three months in a year. Other time of the year, water cannot reach to the lake because of high evaporation, infiltration and usage of the water for irrigation. The land irrigated with the waste water tends to loose its productivity. In this study, water samples were collected and analysed from one hourly period for 2 days (24x2=48), daily period for 3 weeks (7x3=21) and monthly samples for a year (9 months). The samples were analysed either trihalomethanes containing or not, also results were compared with disinfection method that used for drinking water, and samples were collected from ten different points on the channel. Pollution level of the channel water was controlled in accordance with the Turkish Water Pollution Control Law. In addition to trihalomethanes analysis, the effect of aeration on trihalomethanes was investigated .
Collected samples (given above) were analysed for trihalomethanes compounds, and compared the relationship between disinfection type and dosage method on trihalomethanes formation in this study.
Key Words : Chlorinated aliphatics, disinfection, removal, wastewater, chlor.
INTRODUCTION
Chlor used for water disinfection and domestic disinfection with strong oxidise effect.
Furthermore, chlorine and chloramines give a number of substation reaction. Disinfectant formed substation reaction produces too much chloride aliphatic concentration. When the dosage was not controlled on disinfection processes, high remain chlor concentration found in water network system especially near the water container applying hypochloride

1

. Most important by-product is trihalomethanes (THM) after chlor disenfection

2

. Most important source of chlorinated aliphatics is chlorinide processes and solid/liquid wastes of industrial

activities

3

. Chlorine dosage, pH, failure of production of remain chlor and contact period are effective parameters on formation of these compounds

4

. THM levels decrease with decrease in pH values. Oxidation and oxidation product (specially THM’s) increase at high chlorine dosage. A number of investigation showed that contact period of chlorine effected positively formation of chloroform.
Most abundant organic chloride compound in water treatment plat are 1,4diklorbenzen, dichlormetane, chloroform and tetrachloroethylene (PCE). Furthermore some other organic compounds are also found. These chloride methane compound have volatile peculiarity and carcinogenic effect

5

. These compound coming with waste water have effect on decreasing performance ability of mud decay unite or high inhibition degree and stopping activity of unite at least.
PCE is a chlorinated aliphatic compound essentially used in industrial activity. A methanogenic and sulphate-reducing consortium was obtained from anaerobic digested sludge from a waste water treatment plant

6

. Lampron et. al.

7

, an ascending fixed-bed reactor inoculated with this mixed culture was fed semi-continuously with various PCE loading. They found about 98% PCE removal. A study of Lampron et. al. show that an anaerobic culture reductively transformed trichloroethene (TCE) in an aqueous medium containing elemental iron as the sole electron source. TCE disappearance period was increased about 65%, without elemental iron.
There are some aerobic biodegradation of Volatile Organic Compounds (VOC). A basic model of biodegradation for volatile substrates has been developed for the aerobic decomposition of aromatic and aliphatic hydrocarbons

8

. This model predicts an extreme sensitivity of potential biodegradation rates to the air-water partition coefficients of the compounds. However, oxygen transfer is likely to limit aromatic hydrocarbon degradation rates.
THM’s are removal by aeration at advanced treatment method and oxidation (by H
2
O
2
,
KMnO
4
, ClO
2
, O
3
) is method used frequently removal works

9

. Generally air was used for degradations of THM’s. Air was given with conventional bio-filter and aeration by diffusers

10

. About 94% of VOC removal was obtained at bio-filter systems with aeration. About
90% of odour removal also obtained with VOC removal.
In this work, samples were collected and analysed for THM’s at two sets hourly during 24 h period (24x2=48); daily period for 3 weeks (7x3=21) and monthly samples for a year (9 months). The samples were analysed either THMs containing or not, also results were compared the effect of THM’s production with disinfection type and dosage method that used for drinking water disinfection. In addition, the effects of aeration on THM removal were investigated. In the period of first 24 h, dosage of chlorine as sodiumhypochloride was not orderly in the several wells water because water treatment plant was in the attention period. In the second 24h period, daily and monthly sampling, samples were collected after the water treatment plant started. When the water treatment plant was working, about 80% of Konya drinking water requirement was supplied by this plant (2 mgL
-1
Cl
2
gas dosage at pH between
6.5-8 with automatic chlorinating system) and about 20% was provided from the wells.

MATERIAL AND METHODS
The waste water samples were collected from the beginning of Konya Main Discharge
Channel Advancement Centre, hourly period for two days (24x2=48), daily period for 3 weeks (7x3=21) and monthly samples for a year (9 months) in this investigation.
There are three pump station at promotion system. At the beginning of Konya Main
Discharge Channel, first pomp station which test samples are collected for this investigation.
The channel contains mostly domestic waste water and a small amount of industrial waste water. It reaches to the Tuz Lake after 120 km of open channel. The water samples of the channel was kept in coloured, tight 1 litter glass bottle. Hourly and daily water samples were collected on every Wednesday because industrial waste water was expected to reach the channel.
Petroleum ether was used for the extraction of THM’s. Two ml of Petroleum ether was added on 1 L of each sample in the balloon flask separately and shaken for 4 min, then organic phase was separated. Processes was repeated with a second 2 ml of Petroleum ether on water phase. THM’s were analysed by a HP 5890 Series II gas chromatography with a capillary column (HP-624, i.d. 0.25 mm, 30 m, film thickness 1.4 µm) and using electron capture detector (ECD) and flame ionisation detector (FID). Extracted samples were injected to sampling room (column) of the GC by a silicone septum using a hypodermic syringe. The amount of injection was changing between 0.2-0.5 µL

11

. Pressure of carrier N
2
was 5 kg/cm
2
and gas flow rate was 1.4 ml/min. Column was 0.25 mm (i.d.), 30 m length and 1.4
µm film thickness. Processes temperature was oven 240 °C, injector 250 °C and detector 300
°C. Measurement sensitivity was 0.001 µmL -1
.
Secondly artificial water samples were used for investigation of THM removal. 2000 mgL
-1
chloroform, tetrachloroethane, threechloroethene and dichloromethane were added separately each of four flask with 1 L distilled water non containing any THM’s. The water in the flasks were aerated by diffuser for 5 days. Chloroform, tetrachloroethane, TCE and dichloromethane were analysed in daily samples taken from each flasks separately with the method given blow.
RESULTS
Trans1,2-dichloroethene was found only twice in the first set and very high concentrations (84.6 µgL -1
) in the second set. In addition, concentration change was shown a stable character. The changes of Trans1,2-dichloroethene was given in Figure 1.
Dichloroethene was found only in the second set. 1,2 dichloroethene and TCE were compounds found only in the second experiment set. Specially TCE found in eight samples and at low levels (Figure 2).

20
18
16
14
12
4
2
0
10
8
6
1 5 9 13 17 21
Time (h)
Figure 1. Chloride aliphatic concentrations of the first set hourly samples in the outlet of sewage system of Konya (

= PCE;

= T-1,2DCEx4;

=Chloroform).
Chloroform the most toxic compound in other toxic compounds quite frequently was found in both sets. The application disinfection method was manual dosing of sodium hypochlorite in the first set. This was effected the concentration increase of measured compounds at very important level. Automatic dosing of the chlorine gas at suitable condition was used in the second set, whereas qualitative and quantitatively lower levels chloride aliphatic concentrations were found (0.31-1.5
 gL
-1
, Figure 2).
120
100
80
60
40
20
0
1 5 9 13 17 21
Time (h)
Figure 2. Chloride aliphatic concentrations of the second set hourly samples in the outlet of sewage system of Konya (

= Trans-1,2Dichloroethane;

= 1,2Dichloroethane;

=
Dichloromethane).

On the contrary, PCE was present in both sets at low levels with a peak concentrations between 12:00-15:00 o’clock with a range of 0.69-2.67 µgL
-1
in the first set (Figure. 3) and
0.04-1.69 µgL -1 in the second set (Figure 3).
2
1.5
1
0.5
0
1 4 7 10 13 16 19 22
Time (h)
Figure 3. Low levels chloride aliphatic concentrations of the second set hourly samples in the outlet of sewage system of Konya (

= PCE;

= Chloroform;

= TCE)
25
20
15
10
5
0
1 5 9 13 17 21
Time (d)
Figure 4. Chloride aliphatic concentrations in the outlet of sewage system of Konya (1 st week
2-9.12.1997, Ambient temperature: 17.7 o
C, Water temperature: 10 o
C, 2 nd
week
10-17.12.1997, Ambient temperature: 11.8.
25.1997 Ambient temperature: 12 o
o
C, Water temperature: 11, 3 rd
week 18-
C, Water temperature: 11.2 o C) (■ = TCE, 
=
Chloroform; ♦ = Tetrachloromethane; + = PCE; x= Dibromochloromethane; ● =
1,3 Dichlorobenzenx4; o = 1,1,2,2 Tetrachloroethane)

Table 1. Distribution of chloride aliphatic compounds by the month found in samples,
 gL
-1
Compounds TCE Chloroform DCM T1,2 DCE DBCM 1,2 DCE PCE
January
February
March
April
May
June
July
0.1
-
2.5
0.59
- 1.46
0.23 0.52
0.37 0.48
1.1 0.37
0.6 0.40
-
-
-
-
-
- -
52.2 61.5
-
-
-
-
-
-
-
-
-
-
0.05 -
- -
-
36.0
-
-
-
-
0.33
0.19
0.01
0.06
0.07
0.07
August 0.8
September 0.8
0.48
1.02
-
-
-
-
-
-
-
-
0.01
0.01
October 0.1 1.82 - - - - 0.006
DCM; Dichlormethane, DBCM; Dibromochlormethane, T1,2DCE; Trans1,2-dichlorethane,
1,2-DCE; 1,2-Dichloretane, P.S. : (-) is lover than measurable level of equipment.
Table 2. Analysis of Konya Main Discharge Channel Wastewater between January and June months in 1997 [12].
Parameters Analysis Results Discharge
Standards
Sampling Date, 1997 01.01 20.02 11.03 10.04 10.05 11.06
BOD
5
(mgL -1 )
COD (mgL
-1
)
-
-
-
-
672
1020
442
854
487
970
365
750
T. Solid Matter (mgL
-1 ) 1710 540 648 937 570 475
T. Settled Matter (mlL -1 ) 18 20 9 4.5 18 21.5
Suspended Matter mgL -1 ) 348 106 421 246 124 127 pH
Nitrate (mgL
-1
)
Temperature ( o
C)
Oil-Grease (mgL
Zinc (
 gL
-1
)
-1
Copper (
 gL
-1
)
Cadmium (
 gL
-1
)
)
T. Chrome (
 gL
-1
)
Mercury (
 gL
-1
)
7.5
-
10.8
-
87
2
<1
20
1
7.8
-
10.8
-
130
17
<1
69
2.4
7.6
0.25
11.2
284
93
10
<1
10
0.5
7.8
0.32
13
240
-
-
-
-
-
8.3
0.45
13.8
234
-
-
-
-
-
8.2
0.7
15.1
196
-
-
-
-
-
-
4000
-
-
500
6.5-10
-
40
250
10000
2000
2000
5000
200
Turkish standards are not exist for the organic chlorine compounds. For this reason, comparisons were made by the German Standards (DIN). Maximum 200
 gL
-1
limit levels were given for these compounds by the German Standards. The concentration limits of compounds were acceptable levels at comparing with the standards. Except 1,3-diklorbenzen exceeded once to the 200
 gL -1 . Dichloromethane, 1,1 Dichloretylene, Trans-1,2-

Dichloretylene, 1,1 Dichlorethane, 1,2 Dichloretane, 1,1,1 Trichloretane, 1,1,2 Trichlroethane,
1,2 Dichlorpropane were not found in hourly and daily sampling at the measurable levels. To taking consideration of monthly sapling, dichlotomethane, trans 1,2-dichloroethane, 1,2 dichloroethane (in February), and dibromomethane (in March) were resented at 10 month sampling period (Fig. 4).
The values of BOI, KOI, total solid matter, organic matter, TSSM and oil-grease results are over the standards but heavy metals, pH, temperature and nitrate were in acceptable levels (Table 2). In this investigation, three compounds (DCM, 1,2 DCA, TCE) in the 1 st set and six chloride aliphatic compounds (DCM, 1,2 DCA, TCE, tetrachlorethane, chloroform, trans-1,2 dichlorethane) in the 2 nd
set were found. Dichlormethane and chloroform in the compounds given above were highest concentration variation in the 1 st
24 hour sampling. Chloroform was found at wide concentration intervals in the 1 st set (treatment plant was not working) and it was stable concentration variation in the 2 nd
set (treatment plant was working). There was uncontrolled sodium hypochloride dosage in the 1 st
set, automatic dosing of the chlorine gas dosage was applied leaving 0.6 mgL
-1
remand chlorine. These results show the importance of dosage type. Drinking water was obtained by well water because water treatment plant was in general care period during 1 st
24 hourly sampling period.
Number of the chloride aliphatic compounds were seven in the daily sampling period. The most of them were found first week sampling. Most abundant compound were chloroform,
TCE, PCE and 1,4-dichlor benzene in this investigation. Chloroform and PCE were found both sampling period (hourly and daily sampling). Trans-1,2-dichlorethylene, dibromchlormethane and 1,1,2,2-tetrachlorethane were compounds found rarely. TCE, chloroform and PCE were mostly found compound in the monthly sampling.
DISCUSSION
THM’s have been analysed on the 12 samples collected from the route of Konya Main
Waste Water Discharge Channel. Obtained results show that THM’s concentrations were decreased with the distance from the city discharge point. THM was not determined some sampling points. During the removal of THM’s investigation, removal productivity after 4 day aeration was about 95% for chloroform, 94% for tetrachloroethane, 100% for TCE and
915 for dichloromethane (Table 3). Daily removal of THM’s by aeration is given in Figure 5.
Table 3. Removal productivity of THM’s by aeration
Removal of THM/Days 3 Days 3.5 Days 4 Days 4.5 Days
TCE, %
PCE, %
Chloroform, %
Dichloromethane, %
83.0
88.0
84.5
81.0
91.0
92.0
89.0
87.0
100
93.5
94.5
91.0
100
97.5
100
98.0

200
150
100
50
0
0 1 2 3 3.5
4 4.5
Time (d)
5
Figure 5. The removal of THM’s depends on the aeration period (◊ = Dichloromethane; ■ =
Trichloroethane;
○
= Tetrachloroethane; ▲= Chloroform)
Source of THM’s was drinking water chlorinating and also usage of domestic disinfectants contribute to formation of THM’s. Suschka et al.
[13] have found 32 organic compounds in the waste water plants. There are no significant difference between day and night concentrations. Only three compound were detected in the 1 st
set of analysis in our investigation. This result shows that chlorinated aliphatic compounds arise from chlorinating unite, afterwards and waste water, there is no significant effect of industrial waste water on the production of these compounds. In addition, similar number of the compounds were not found in the both 1 st
and 2 nd
sampling sets in our investigation, this shows the chlorinating compounds (gas chlorine, hypochloride ect.) have different mechanism on the formation of chlorinated aliphatic compounds.
The sources of present pollution potential of the Konya Main Waste Water Discharge
Channel were domestic and industrial waste water and rain water. On the other hand, when pollution was investigated for THM, pollution sources must be different. As the first step results of investigation, important source of chlorinated aliphatic compounds was reaction products between remind chlorine given at drinking water treatment plant for disinfection and organic mater of domestic waste water. Chlorinated aliphatic compounds produced from reaction between chlorine of drinking water chlorinating and afterward organic matter in the water can reach until discharge point. Humic matters are the premier materials producing
THM’s and chlorinated aliphatic compounds. In addition to water treatment plants, usage of the chlorinated compounds for the cleaning constitutes a source for the THN’s. Investigated chlorinated aliphatic compounds arise mostly from the chlorinated aliphatics used for either water disinfecting or domestic cleaning materials [14].
Some investigations have postulated that aeration deformed the chlorinated aliphatics.
In addition, chlordioxide (ClO
2
) was used for a disinfecting materials as a alternative to chlorine recently, because it is a good disinfectant and not combines with ammonia.

Chlorinated aliphatic compounds concentration reduce and disappear with discharging of waste water in the long distance of open channel. It is still not clearly known effect of the waste water usage for the watering in the agriculture on the soil and products.
Measurements of parameters BOD, COD, total solid matter, organic matter, total suspended matter and oil-grease values other than chlorinated aliphatic were not exceeded to the limits of Table 25 in the Turkish Environment Regulation. Nitrite, pH, temperature and heavy metals are also acceptable levels according to limits. However, the values of the parameters given above are not pass over the limits of Table 25, they are compared with the characteristics of big cities Ankara, Istanbul, Adana. The values of BOD and COD are quite high. Purpose of these result, concentration of some parameters were increasing with the drainage of the sewage system with slow flow rate, because it very old system. Usage of the liquid waste irrigation of garden and giving concentrated waste water to sewage system was increased organic matter concentration. Heavy metal concentrations were also lover than limits due to most of the waste water content originating from domestic waste water.
REFERENCES
1.
Toprak H., Izmir Kenti Içme Suyu Şebekesinde Uygulanan Klor ile Dezenfeksiyon
Işleminin Incelenmesi, 1. Uludağ Environmental Engineering Symposium, Bursa, 21-
30 (1996).
2.
Montgomery J.M., Water Treatment Principles and Design, John Wiley and Sons Inc.,
USA. (1985).
3.
Galapate R.P., Kitanaka I. K., Mukai T., Shoto E. and Okada M., Origin of
4.
5.
Trihalomethane Precursors in Kurose River Hiroshima, Water Science & Technology ,
35, 15-27 (1997).
Singer P.C., Complying With Trihalomethane Reduction Requırements in Water
Treatment Facilities, Pollution Technology Review , 167 (1989).
Graham N.J.D., Wardlaw V.E., Perry R, and Jiang J.Q., The Significance of Algae as
6.
7.
Trihalomethane Precursors, Water Science & Technology , 37, 83-89 (1998).
Cabirol N., Jacob F., Perrier J., Fouillet B. and Chambon, P., Complete Degradation of
High Concentrations of Tetrachloroethylene by a Methanogenicconsortium in a Fixed-
Bed Reactor, J. Biotechnology , 62, 133-141 (1998).
Lampron K. J., Kyle J., Pei C. C. and Daniel K. C., 1998, Biological Reduction of
8.
Trichloroethene Supported by Fe(0), Bioremedation J.
, 2, 175-781 (1998).
Hunt J. R., Holden P. A., Coupling Transport and Biodegradation of VOCs in Surface and Subsurface Soils, Environmental Health Perspectives Supplements , 103, 75
9.
(1995).
Mowry B.A., Threatment Technology to Meet the Drinking Water Standards for
Trihalomethanes for Jackson, Ph.D., Mississippi State Unv. (1982).
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Finn L., Spencer R., Managing Biofilters for Consistent Odor and VOC Treatment
(Cover Story), BioCycle , 38, 40 (1997).
11.
Hışıl Y., Enstrümantal Gıda Analizleri-II, Printed in the Ege University, Izmir-Turkey
(1994).

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Anonymous, Turkish Environment Regulation, Türk Çevre Vakfı Press., Ankara-
Turkey (1992).
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Suschka J., Mrowiec B. and Kuszmider G., Volatile Organic Compounds (VOC) at
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
Technology , 33, 273-276
(1996).
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Özdemir C., Dorum A., Konya Kanalizasyonunda Klorlu Alifatikler Üzerine Bir
Çalışma, J. Selcuk Unv. Eng.-Agr. Faculty , 12, 9-15 (1997).

LIST OF FIGURES
Figure 1. Chloride aliphatic concentrations of the first set hourly samples in the outlet of sewage system of Konya (

= PCE;

= T-1,2DCEx4;

=Chloroform).
Figure 2. Chloride aliphatic concentrations of the second set hourly samples in the outlet of sewage system of Konya (

= Trans-1,2Dichloroethane;

= 1,2Dichloroethane;

=
Dichloromethane).
Figure 3. Low levels chloride aliphatic concentrations of the second set hourly samples in the outlet of sewage system of Konya (

= PCE;

= Chloroform;

= TCE)
Figure 4. Chloride aliphatic concentrations in the outlet of sewage system of Konya (1 st
week
2-9.12.1997, Ambient temperature: 17.7 o C, Water temperature: 10 o C, 2 nd week
10-17.12.1997, Ambient temperature: 11.8.
25.1997 Ambient temperature: 12 o
o
C, Water temperature: 11, 3 rd
week 18-
C, Water temperature: 11.2 o C) (■ = TCE, 
=
Chloroform; ♦ = Tetrachloromethane; + = PCE; x= Dibromochloromethane; ● =
1,3 Dichlorobenzenx4; o = 1,1,2,2 Tetrachloroethane)
Figure 5. The removal of THM’s depends on the aeration period (◊ = Dichloromethane; ■ =
Trichloroethane;
○
= Tetrachloroethane; ▲= Chloroform)

14
12
10
8
6
4
2
0
20
18
16
1 5 9 13 17 21
Time (h)

120
100
80
60
40
20
0
1 5 9 13 17 21
Time (h)

2
1.5
1
0.5
0
1 4 7 10 13 16 19 22
Time (h)

25
20
15
10
5
0
1 5 9 13 17 21
Time (d)

200
150
100
50
0
0 1 2 3 3.5
4 4.5
Time (d)
5