DISINFECTION EFICIENCY TRIHALOMETHANES (THMs) FORMATION AFTER CHLORINATION PROCESS

Dumitru RISTOIU1, Melinda-Haydee KOVACS1, Iovanca HAIDUC1, Sidonia Vancea2

1 Babes Bolyai University of Cluj-Napoca, Faculty of Environmental Science, Str. P-ta Stefan cel Mare, no.4, 400084, Cluj-Napoca, email: dristoiu@enviro.ubbcluj.ro 2 Garda de Mediu, Comisariatul Judetean Cluj, str. G-ral T. Mosoiu, nr. 49, Cluj-Napoca, Romania.

ABSTRACT Chlorine is one of the most common disinfectant agents in water disinfection process in Romania. The goal of the water disinfection is to protect the water in the distribution systems against microbial contamination and to prevent and control re-growth of microorganism in the water distribution system. The major disadvantages of chlorination process are the formation of disinfection by-products (DBPs) like trihalomethanes (THMs). Those DBPs are suspected to have diverse negative effects on human health, in specially carcinogenicity and birth defects. In this study is presents the monitoring results at the Water Treatment Plant (WTP) from Gilau in the period of March 2006 August 2007. Also was monitored the seasonally variations of THMs formation. THMs formation during disinfection of drinking water depends on various parameters as pH, temperature, natural organic matter, and ammonium and chlorine exposure. To assess the influence of seasonal variances in these parameters, laboratory experiments were performed monthly with filtrated water from the WTP Gilau, Romania. Also it was determinate the THMs and chlorine kinetics in the particular water matrix which would enable to predict THMs formation on easier measurements of chlorine consumption. The obtained results were also used to assess disinfection efficiency under typical treatment conditions. Introduction Chlorination has made Cluj water supply safe from illness-producing microorganism such as bacteria and viruses. That technology has almost completely eliminated from our lives the risk of waterborne diseases such as typhoid fever, cholera, and dysentery. But, the health benefit of chlorination has introduced some possible risks from the by-products of the disinfection process. The DBPs (disinfection by-products) were produced during the disinfection process. As the DBPs were investigated, scientists also discovered the harmful health effects of these halogenated byproducts on animals and humans [1]. One class of these DPDs is trihalomethanes (THMs) that appear in treated water after chlorination process, when chlorine reacts with natural organic matter (NOM) present in all type of water [2, 3, 4, 5]. 146

The concern surrounding THMs formed during disinfection process is based on evidence that these by-products have some adverse health effects, in particular cancer and reproductive disorders [6]. Since, the discovery, and because the source and routes of human exposure of THMs could de: drinking water (ingestion), bathing (ingestion, inhalation, dermal), showering (ingestion, inhalation, dermal), swimming pool use (ingestion, inhalation, dermal), foods and beverages (ingestion) several regulation have been promulgated by the regulation agencies of various countries to monitor and control THMs. Various country governmental health protection agencies have focused on THMs and promulgated regulations for THMs as shown in table 1 [7]. In Romania the regulation and monitoring of THM has became a current issue in connection with Romanias entry to the UE and the fulfillment of the required drinking water standards. In order to minimize cancer risk, the Romanian has adopted the maximal permissible value fixed in the EU drinking water directive has been adopted by the Romanian legislation in 2002, granting the water companies a transition time of 10 years to meet the requested standards and accepting in the first 5 years a TTHM value of 150 g/l [8, 9, 10]. Table 1. Standards/Guidelines related to THMs (mg/l) in various jurisdictions of World (Sadiq and Rodriguez, 2004) Compounds WHO USEPA (2001) Health Canada AUS-NZ UK (1993) (2001) (2001) (2000) CHCl3 0.200 0.000* CHCl2Br 0.060 0.060* CHClBr2 0.100 0.000* CHBr3 0.100 0.000* TTHMs 0.080 0.100 0.250 0.100 (THM/WHO)1** * Maximum Contaminant Level Goals (MCGL) ** the sum of the ratios of the THM levels to the guideline values should not exceed 1.

Materials and methods The water treatment plant Gilau is located about 18 km to the west of the Cluj-Napoca city and provides drinking water for the approximately 600 000 inhabitants of Cluj-Napoca. Its principal water sources are the storage lakes Gilau and Somesul Cald River. The water disinfections in water treatment plant from Gilau are obtained through addition of chlorine gas. In WTP Gilau the chlorine dose is regulated manually to achieve a free chlorine concentration at the exit of reservoir (where the water arrives approximately 12 minutes after chlorination) of 0.5 0.7 mg/l in winter season and 0.7 0.9 mg/l in summer season. During the study several samples were collected monthly from different sampling point in WTP Gilau and distribution system in Cluj-Napoca. The sampling contains raw water, filtrated water after one of the sand filters and treated water with chlorine. The water sample was collected once a month started with March 2006 to 2007 July. The samples were stored in 40 ml vials and closed with Teflon lined screw cap, preserved with sodium thiosulfate (Na 2S2O3) at 40C until the analysis. All samples were measured between in 1 and 7 days after sampling. For kinetics experiments filtrated water (after one of the sand filters) were taken monthly from WTP Gilau. The filtrated water was stored in 5 L plastic bottles at 4 0C until the chlorination experiment and 147

without adding any preservatives. In laboratory, kinetic experiments were carried out after the chlorination of the filtrated water samples [11]. THMs were carried out by Thermo Finningan U.S.S. Trace GC Ultra gas chromatography with electron capture detector (GC-ECD) with TriPlus HS auto sampler. The analysis was made using headspace technique. 10 ml of sample was filled into 20 ml headspace vials and closed with Teflon lined screw cap. After that the samples were equilibrated in an oven at 60 C for 45 minutes, 1 ml of the headspace was then injected into the GC (Cyanopropylphenyl Polysiloxane column, 30 m x 53 mm, 3 m film thickness, Thermo Finnigan, USA). The column program was 35 C (hold time 3 minutes), 15 C/minutes to 200 C (hold time 3 minutes). The inlet was set at 200 C. The calibration standards were prepared using the THM test mixture produced by Restek. The calibration standards were prepared for the range 0 100 g/L in pure water. In the analysis of THMs samples, samples of 1 mL volume of headspace were injected into the GC column with TriPlus HS auto sampler and four peaks were detected belong to the four THM compounds. In kinetics experiments beside THMs compounds also the chlorine ion concentration was measured calorimetrically according to standard method 8021 DPD method (powder pillow) for free chlorine determination and standard method 8167 DPD method (powder pillows) for total chlorine determination using a Hach Dr 2800 analyzer. A 25-ml cell was filled with samples and added DPDs free chlorine reagent (powder pillow). After mixing, chlorine ion concentration was read at 530 nm wavelength. Laboratory chlorination experiments were carried out monthly with filtrated water collected at the treatment plant. The experiments were conducted under two conditions: base line condition (pH 7; 21 C and 2.5 mg/l Cl2) to gain information about the change of the organic matter in the raw water [12-14]. The second condition was: seasonally variable condition to simulate the actual process at the treatment plant [15-17]. Experiments under seasonally variable conditions were carried out with the pH and temperature as measured in the pretreated water on the sampling day (see table 2) and the chlorine dose added in the experiments were the same as in the sampling day at the treatment plant Gilau. Table 2. Filtrated water properties (pH and temperature) in the treatment plant WTP Gilau on the sampling day Year 2006 2007 Month pH Temperature (C) Month pH Temperature (C) March 7.4 4 January 7.7 8 April 7.2 4 February 6.6 6 May 7.3 8 March 7.4 7 June 7.1 8 April 7.3 7.5 July 7.0 12 May 7.2 9 August 7.3 14 June 7.4 8 September 7.2 13.5 July 7.2 11 October 7.0 14 August 6.9 14.5 November 7.0 9 September 7.0 12 December 7.0 7 October 7.0 7

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Results and discussions CHCl3 was the most determinate trihalomethanes species observed after the chlorination of reservoir water in all of the sampled months. In all of the sampling point the CHCl3 concentration and total trihalomethanes concentration did not exceed the maximum permissible value (100 g/l). Also the CHCl3 formation rates in the distribution system of Cluj-Napoca have a high seasonal variability see figure 1.
THM measurement in Cluj

july 2006 aug.06 september 2006 oktober 2006 november 2006 december 2006 january 2007 february 2007 march 2007 april may

may april march 2007 february 2007 january 2007 december 2006 november 2006 oktober 2006 september 2006 aug.06 july 2006

Figure 1. Chloroform concentration in WTP Gilau and distribution system from Cluj presented in function of distance started with 1 what is raw water to 8 that is located in the distribution system in Cluj after 18 km from WTP Gilau (1 Raw water, 2 Filtrated water, 3 Sampling point Chlorinated water, 4 Sapca Verde, 5 Beer factory, 6 Chemistry faculty, 7 Institute of Public Health and 8 Environmental Faculty)
80 70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8

During the laboratory experiments it was observed that while THM formation increases, chlorine concentration decreases with increasing time due to the chlorine reaction with organic precursors to form THMs (see figure 2 and 3).
Total chlorine kinetoics 2006 under seasonally variable conditions
martie aprilie iunie iulie august septembrie octombrie noiembrie decembrie Series11 mai

CHCl3 (ug/l)

THM kinetics 2006 - seasonally variable condition

80 70 60
martie aprilie mai iunie iulie august septembrie octombrie noiembrie decembrie

1.8 1.6 1.4 Total chlorine (mg/l) 1.2 1 0.8 0.6 0.4 0.2 0 0

CHCl3 (ug/l)

50 40 30 20 10 0

100

200

300

400

500

600

700

100

200

300

400

500

600

700

Time (minutes)

Time (minutes)

Figure 2. Total chlorine kinetics in different month in 2006 under seasonally variable 149

condition where the pH, temperature and

chlorine dose is the same as in the sampling day for every month of the study. Figure 3. Chloroform kinetics in 2006 for different month under seasonally variable

condition where the pH, temperature and chlorine dose is the same as in the sampling day for every month of the study.

For a given initial chlorine dose, the formation of THMs and consumption of chlorine were both completed at the same reaction time, however, the time period required for the completion of THM formation varied with the applied chlorine dose and season (see table 3). Table 3. Temperature and Chlorine dose required for different month in 2006 and 2007. Year 2006 2007
Month Chlorine dose (mg/L) Temperature (C) Month Chlorine dose (mg/L) Temperature (C)

March April May June July August September October November December

1.5 1 1.2 1 1.4 1.5 1.6 1.4 1.3 1.1

4 4 8 8 12 14 13.5 14 9 7

January February March April May June July August September October

1.1 1 1.1 1.2 1.1 1.2 1.4 1.3 1.1 1

8 6 7 7.5 9 8 11 14.5 12 7

At high chlorine doses, THM formation was complete earlier than that for the low doses due to the fact that initial chlorine concentration is an important factor affecting the time of completion of the reaction as well as the amount and rate of THM formation (higher values of initial chlorine also results in higher reaction rates) see figure 3 and table 3. The reaction rates of chlorine are dependent on several factors such as source water characteristics, treatment type, contact time and the characteristics of the distribution system. Besides the kinetics of THM formation, consumption of chlorine was also investigated. Chlorine consumption and THM formation were very rapid during the first hours of the reaction followed by a more gradual decay and formation after 7 hours see figure 3. The rapid and slow decay rates are likely due to different competing reactants, such as the oxidation of inorganic compounds (rapid) and substitution reactions with NOM (relatively slow). Because one of the most important factors affecting THMs, respectively chloroform formation during the disinfection procedure is reaction time it was investigated the influence of reaction time on trihalomethanes formation in Gilau WTH and distribution system. Is critical in order to determine the final concentrations to which people could be exposed. The kinetics of the formation of trihalomethanes can be different, depending on the chlorine dose, water pH, water temperature and organic matter content. In figure 4 is presented the relationship between chlorine consumption and chloroform formation under seasonally variable conditions. The concentration of chloroform obtained in chlorination experiences under seasonally variable conditions were linked to the chlorine consumption. The resulting linear correlation was R2 = 0.8742. This could be explained by the 150

changing composition of the organic matter and the varying ammonium concentration in the raw water: ammonia reacts rapidly with free chlorine to chloramines witch shows much lower reactivity with organic substances. For the same chlorine consumption higher ammonium concentration therefore leads to lower THM yields.
40 35 30

y = 33.323x + 1.1685 R2 = 0.8742

CHCl3 (ug/l)

25 20 15 10 5 0 0 0.2 0.4 0.6 0.8 1 1.2

Chlorine consumption (mg/l*min)

Figure 4. Relationship between chlorine consumption and chloroform formation under seasonally variable conditions. NH2Cl concentration was subtracted from the chlorine concentration. Chlorine consumption was very rapid during the first hours of the reaction followed by a more gradual decay after 4 hours. The decay rate constants obtained with the filtrated samples was between 0.06681 and 0.1743 min-1. The actual levels of THMs in drinking water vary greatly depending on temperature, organic matter nature and concentration, applied chlorine dose, pH, reaction time and inorganic ions like bromide. Conclusions CHCl3 was the most determinate trihalomethanes species observed after the chlorination of reservoir water in all of the sampled months. In all of the sampling point the CHCl3 concentration and total trihalomethanes concentration did not exceed the maximum permissible value (100 g/l). The THMs formation rates in the distribution system of Cluj-Napoca have a high seasonal variability. Trihalomethanes concentration depended on the applied initial chlorine concentration, water temperature and water pH. Although both low and high chlorine doses are higher than the chlorine demand of the water samples, as the chlorine dose was increased, more chloroforms formed. THMs values measured at high chlorine doses were always higher than the ones measured at low chlorine doses in water treatment plant from Gilau waters from all of the sampled months. For a given Cl2 dose, the formation of THMs and consumption of Cl 2 were both completed at the reaction time, however, the time period required for the completion of THMs formation varied with the applied chlorine dose and season. At high chlorine doses, THM formation was complete earlier than that for the low doses due to the fact that initial chlorine concentration is an important factor affecting the time of completion of the reaction as well as the

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amount and rate of THM formation (higher values of initial chlorine also results in higher reaction rates). Residual chlorine concentration during the completion of THM formation, the overall yield values (TTHM/total Cl2 consumed during the entire reaction periods) as well as the average yield values (g TTHM formed/mg Cl2 consumed between two reaction times) differ trough sampled months that may be attributed to the variations in the nature of organic matter. In all the months, the formation yields were highest during the first hours of reaction time and then showing the rapid THM formation and chlorine decay. References 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. Arora, H., LeChevallier, M. W., Dixon, K.L. (1997). DBP occurrence survey. Journal of American Water Works Association, 89, (6), 60 68. Chen, W. J., and Weisel, C. P. (1998). Halogenated DBP concentrations in a distribution system. Journal of American Water Works Association, 90 (4), 151-163. Marhaba, T. F., and Washington, M. B. (1998) Drinking water protection and byproducts: history and current practice. Advances in Environmental Research, 2, 103115. Morris, J. C. And Baum, B. (1998). Precursors and Mechanisms of Haloform Formation in the Chlorination of Water Supplies. Water Chlorination: Environmental Impact and Health Effects, 2, Ann Arbor, MI. Nikolaou, A.D., and Lekkas, T.D. (2001). The Role of Natural Organic Matter during Formation of Chlorination By-products: A Review, Acta hydrochim. hydrobiol. Vol. 29, (23), 6377. Hsu, C. H., Jeng, W. L., Chang, R. M., Chien, L. C., and Han, B. C. (2001). Estimation of potential lifetime cancer risks for trihalomethanes from consuming chlorinated drinking water in Taiwan. Environmental Research Section A 85, 77-82. USEPA (2001). National primary drinking water standards, United States Environmental Protection Agency, EPA; 816-F-01-007. Guvernul Romaniei (2004): Hotarare pentru aprobarea Normelor de supraveghere, inspectie sanitara si monitorizarea a calititii apei potabil. 669/26.VII.2004. Annex 1, table 1 2. Parlamentul Romaniei (2002): Lege nr. 458/2002 privind calitatatea apei potabile. Annex 1, table 3. Parlamentul Romaniei(2004): Lege nr.363/2004 pentru modificarea si complementarea Legii nr.458/2002. Annex 1, table 2. Adin, A., Katzhendler,v J., Alkaslassy, D., Rav-Acha, C. (1991). Trihalomethanes formation in chlorinated drinking water. A kinetic model. Water Research, 25, 7, 797-805. Duong, H. A., Berg, M., Hoang, M. H., Pham, H. V., Gallard, H., Giger, W. and Gunten, U. (2003). Trihalomethane formation by chlorination of ammonium- and bromide-containing groundwater in water supplies of Hanoi, Vietnam. Water Research, 37, 3242 3252. Edzwald, J. K., Becker, W. C. And Wattier K. T. (1985). Surrogate parameters for monitoring organic matter and THM precursors. Journal of American Water Works Association, 77 (4), 122-132. Elshorbagy, W. E., Abu-Quadis, H., Elsheamy, K. (2000). Simulation of THM species in water distribution systems. Water Research, 34, 3431-3439.

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15. Fayad, N. M., (1993). Seasonal variations of THMs in Saudi Arabian drinking water. Journal of American Water Works Association, 85, 46-50. 16. Gallard, H. and von Gunten, U. (2002). Chlorination of Natural Organic Matter: Kinetics of chlorination and of THM Formation. Water Research, 36, 65-74. 17. Gang, D. (2001) Modeling of THM and HAA Formation in Missouri Waters Upon Chlorination. Phd. Thesis, University of Missouri, Columbia.

The best poster awarded students are:

Ambassade de France 15 jours , Montpellier Milo NENADOVI, Institut VINA Serbie 15 jours , Paris ; Sneana MILOVANOVI, Institut VINA Serbie Institut de Vina et Chambre de Commerce 7 jours France ; Vesna DJORDJEVI, Chaire SIMEV UNESCO 7 jours Montpellier, Melinda KOVA, Acadmie des Sciences 3 jours France ; Aleksander TRAJCE, Volia Environnement Sant 3 jours Paris ; Acad Sciences, Bulgarie, Pavlova ANGELOVA Institut VINA Serbie Univ.Cluj-Napoca, Roumanie Univ. Tirana, Albanie Institut de leau,

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