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Desalination 21 3 (2007) 18

Physicochemical and microbiological characteristics of the potable water supply sources in the area of Kozani, Western Macedonia
Elisavet Amanatidoua*, Kalliopi Adamidoub, Eleni Trikoilidoub, Foteini Katsioulib, Olga Patrikakib, Lazaros Tsikritzisa
a

Technological Educational Institute of Western Macedonia, Koila Kozanis, Kozani 50100, Greece Tel. +30-2461040161 ext. 300; email: eamanatidou@teikoz.gr b Purely Prefectional Enterprise of Kozani Environmental Centre, 1st Km Ptolemaidas-Kozanis, Ptolemaida 50200, Greece
Received 20 January 2006; revised accepted 3 May 2006

Abstract In the present study, the physicochemical and microbiological characteristics of the potable water in the prefecture of Kozani are studied, according to the results of the analysis carried out in the Environmental Centre Laboratory, during 20022005. According to the Greek Legislation and the EU Directive for potable water, a water quality monitoring program was created for the County of Kozani, and the parameters of the Check and Audit Monitoring were examined for a number of samples from selected samples sites at regular intervals. Conclusions relative to the water adequacy of springs and drills, water tanks and supply network, as well as the possible reasons for water quality problems are presented in the study. Generally, the water quality depends on its chemical and microbiological condition. In the areas with penetrable formations and agricultural activity, the nitrates presence was observed in relatively stable concentrations in time. The water is easily infected during its transportation from the source to the internal water supply network and finally to the consumer. The condition of the water supply networks is a factor which contributes to the water quality. Keywords: Potable water; Quality; Monitoring; Kozani

1. Introduction The ensuring of good quality drinking water is a basic factor in guaranteeing public health, the
*Corresponding author.

protection of the environment and sustainable development. The Directive 2000/60/EC [1] for water resources and its Greek version N. 3199/9-12-2003 and Y2/2600/2001 [2,3], impose the organization

Presented at the International Conference on New Water Culture of South East European Countries-AQUA 2005, 2123 October 2005, Athens, Greece.
0011-9164/06/$ See front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2006.05.053

E. Amanatidou et al. / Desalination 213 (2007) 18

of monitoring networks for a variety of quality and quantity parameters of potable water and aquatic systems. The objective of the current study is to present the quality of the drinking water supply sources in the county of Kozani, as well as the comparative evaluation of the physicochemical and microbiological analysis results for the last three years (20022004). The facts resulting from the research saw a continuous reduction in the non-suitable drinking water samples because specific protection actions were taken from the local administration, the responsible authority for preserving the good quality of potable water. The analysis took place at the laboratory of the Environmental Centre (KEPE) of the Prefecture of Kozani, which is responsible, according to agreements with the local municipalities and the Municipality Union, for analyzing the potable water of the County. 2. Materials and methods During the period 20022003 the parameters that belonged to the Routine Analysis were analyzed, according to the Ministry of Health and Social Services legislation [4,5] about the frequency of the sampling and the quality of drinking water [6]. During 2004 the parameters of the Check Monitoring and the Audit Monitoring were analyzed according to the national and European relevant legislation about the quality of water used for human consumption [3,7]. The testing took place at selected sites with techniques for sampling and analysis methods according to the Standard Methods, APHA 1998 [8], the relevant ISO [912], the international recognized manuals [13], and the requirements of the Quality System according to ISO 17025 [14] of the Environmental Centers laboratory. Accredited or controlled equipment was used for analysis. An accredited photometer Hittachi U-2001 for ammonia, nitrite and nitrate analysis was used. Also for turbidity a Dr. Langer NEPHLA

454 turbidimeter, for conductivity a Mettler Toledo MX300 conductivity meter, for pH a WTW INOLAB pH meter and for residual chlorine analysis a LaMOTTE 1200 Chlorine residual meter, were used. The process that was followed for taking the final measures is given below: (1) Formation of a monitoring program and determination of the sampling sites at the beginning of every year. (2) Realization of the sampling program as it is formatted and laboratory analysis of the samples for the selected parameters. (3) Repeat of the sampling program when and where a divergence is observed, with new sampling. (4) Informing the authorities and public and submission of proposals for the improvement of the current situation. (5) Selected parameters analysis and editing of the analysis certifications and Reports/ Technical Essays on behalf of the Municipality Authorities and observance of electronic files. The sampling is carried out according to the monitoring program at selected sites, the program is formatted at the beginning of every year, by taking into account the legislation mentioned above, with the co-operation of the municipalities. The realization of the sampling program secures the necessary conditions for prompt and reliable sampling and transportation of samples. If a divergence of the parameters limits is observed, the sampling and the analysis are repeated. For the period 20022003, according to the relevant legislation, the sampling sites for every settlement are the springs and the drills, the external supply network, the water tanks and the internal supply network. From the internal network, the samples were taken from the top, middle and lower point of each water supply line, as well as from sites where it is possible to have stagnant water for a long period of time. From

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2004 the sampling sites include the water tanks (main point) and the consumers tap. The number of samples and sampling frequency is in proportion to the water consumption. A sampling report is filled in before the sampling, in which the sanitary recognition of the area is also included. At the same time the parameters that need in situ analysis are realized such as temperature, pH, residual chlorine including conductivity. These parameters are recorded on the in situ analysis report. 3. Results and discussion 3.1. Water analysis 3.1.1. Physical and chemical water parameters The concentrated results of the physicochemical analysis, from water tank and internal supply networks samples, for the period 20022004 are shown in Table 1. From the observation of the results it can be seen that the averages do not

exceed the limits indicated by the legislation, although there are divergences, according to the recorded maximum values. The cases of the lower and the higher conductivity measurement (24 S/cm at 20C and 3110 S/cm at 20C) are not estimated in the calculation of the average value. Drills and springs water samples from all the county ware analyzed for the same period. Around 10% of the drills was exceeding the nominal limits for some parameters while it was 0% the springs. The precision and uncertainty of all the physicochemical methods was calculated and ranged in the relevant standard methods acceptable limits. The number of samples and their undrinkable percentage per year and per parameter are shown in Table 2. The undrinkable percentage of nitrite, nitrate and ammonium ions varies mostly due to the gradual geographical expansion of the sampling in the county of Kozani as well as and to the increasing number of water samples during 2004.

Table 1 Concentrated results of the physicochemical analysis 20022004 Number of samples Physicochemical analysis 1128 1134 1134 861 Parameter Conductivity pH Turbidity Residual chlorine Ammonium Nitrite Nitrate Unit S/cm at 20C pH units mg/L SiO2 mg/L Minmax 281823 6.98.5 0.061.2 00.8 Average 480 7.45 0.4 0.3 Limit 2500 6.5 9.5 No common alteration Min 0.5 tank Min 0.2 network 0.5 0.5 50 Method of analysis 2510-B 20th Ed. 1998 4500-H + B 20th Ed. 1998 2130 B 20th Ed. 1998 4500-Cl G 20th Ed. 1998 4500-NH3 F 20th Ed. 1998 4500-NO 2 B 20th Ed. 1998 4500-NO 3 B 20th Ed. 1998

1179 1164 1160

mg/L mg/L mg/L

01.98 00.067 0.29207

0.45 0.003 35.7

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Table 2 Number of samples and their undrinkable percentage for the period 20022004 Parameters 2002 Number of samples Nitrate Nitrite Ammonium Turbidity Conductivity pH 121 141 141 121 121 121 Undrinkable percentage 2.5 24.1 12.8 0.8 0 0 2003 Number of samples 255 238 236 230 224 230 Undrinkable percentage 7.9 12.6 8.4 0.9 0 0 2004 Number of samples 784 785 802 783 783 783 Undrinkable percentage 5.7 22.2 17.3 1.2 0.4 0.1

According to the table, the percentages of 2004 are the most representative because they include sampling from almost all around the county. A relatively high percentage of nitrate and ammonium concentrations are observed which indicates mainly recent and seasonal pollution. In the same period a relatively low percentage of increased nitrate concentration is observed in a few areas. In Fig. 1 an example of the nitrate concentration range at a County of Kozani settlement, with continuous limit excess is shown. The divergences are stable for all the period of the measurements and consistently exceed the limit given by the legislation, which means that the problem is permanent and needs solution.
70 Concentration (mg/L) 60 50 40 30 20 10 0
NO3 Limit

3.1.2. Water microbiological parameters The concentrated results and microbiological methods analysis, from water tank and internal supply networks samples, for the period 2002 2004 are shown in Table 3. We observe that the average of total coliforms, E. coli and the total bacteria at 37C, exceed the legislation limits. Drills and springs water samples from all the county were analyzed for 20022003 period. Total coliforms were detected to around 50% of the drills and springs samples. The number of the samples and their undrinkable percentage per year and per parameter are shown in the Table 4. A decrease in the undrinkable water percentage during the measurement period is observed. This is due to the increased information and the conforming of the municipalities with the legislation on the systematic and not occasional water monitoring, the maintenance, frequent cleaning, and installation of disinfection systems in the water tanks and the networks, the adoption of measures for the protection of the supplying systems, etc. In many cases the problem remains and its solution often requires replacement of the water tanks and supply networks, which has a high cost. The above is reinforced also by the fact that microbiological infection is relatively easily and immediately controlled, in contrast with

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Fig. 1. Range of the nitrate ion during 20032004 in a settlement of the County of Kozani.

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Table 3 Concentrating results of the microbiological analysis for 20022004 Check monitoring Parameter Microbiological parameters Total coliform Escherichia coli Total bacteria at 22C Total bacteria at 37C Unit No./100 mL sample No./100 mL sample No./mL sample No./mL sample Minmax 0 to >100 015 0 to >100 0 to >100 Average 10 3 85 25 Limit 0 0 100 20

Analysis method ISO 9308-1:2000 ISO 9308-1:2000 ISO 6222:1999 ISO 6222:1999

physicochemical pollution, which requires a lot of time and money to be dealt with and often results in a search of new water supply sources.

3.1.4. Water tanks and supply water network situation In Tables 5 and 6 the percentage of undrinkable samples for three representative parameters, from the water tanks and water supply systems of the Kozani settlements are presented. The observed range of the undrinkable percentage for these parameters is mostly due to the gradual geographical expansion of sampling in the county, as well as to the increase in water samples. The data from Tables 26 show: The undrinkable percentages, for the nitrate concentration of the water tanks and the supply networks samples, have no essentially difference. In the areas with increased nitrate concentrations, a relatively stable exceed from

3.1.3. Determination of heavy metals, benzolium, pesticides, polycyclic aromatic hydrocarbons and total tri-halogen-methanes From the beginning of the year 2004 fourteen water samples were taken and a total number of 60 parameters like heavy metals, benzolium, pesticides, polycyclic aromatic hydrocarbons and total tri-halogen-methanes, were examined for each sample. In this period no concentrations of the above parameters were detected.

Table 4 Number of sample and undrinkable percentage because of the microbiological parameters Parameter 2002 Number of samples Total coliform 100 mL E. coli 100 mL Total bacteria at 37C 1/mL Total bacteria at 22C 1/mL Intestinal enterococci 100 mL Fecal coliforms 100 mL 140 88 76 140 Undrinkable percentage 44.3 44.3 23.7 24.3 2003 Number of samples 338 301 197 302 Undrinkable percentage 19.2 19.3 9.6 19.3 2004 Number of samples 826 826 797 542 471 Undrinkable percentage 17.5 15.4 10.3 16.6 24.6

6
Table 5 Water quality of water tanks
2002

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2003

2004

Sum Undrinkable Undrinkable Sum Undrinkable Undrinkable Sum Undrinkable Undrinkable percentage percentage percentage Parameters Nitrate 38 Ammonium 34 Total 42 coliform 100 mL 0 3 23 0 9 55 106 93 142 18 11 106 17 12 75 408 408 394 30 38 264 7 9 67

the limits is observed (Fig. 1). The pollution caused from nitrates comes mostly from agricultural activities. A small decrease of ammonium, which is mainly an indication of recent pollution, in the water tanks samples is observed in relation to the total undrinkable percentage, which may be caused via by their partial oxidation to nitrite and nitrate, during their transportation in the external water supply network as well as by their transformation in chloramines, due to the chlorination of the water tanks, depending on the pH value, temperature, initial chorine-tonitrogen ratio, absolute chlorine demand and reaction time [8,15,16]. A small increase of ammonium cconcentration in the water samples from the internal supply network is observed in comparison to those of the water tanks. This occurs because of the low residual chlorine
Table 6 Water quality of the internal supply network
2002 2003

concentrations measured, in combination with the situation of the water supply network. An important increase of total coliforms is observed, especially in the water tanks, in comparison to the total undrinkable percentage, which indicate that the supply sources situation and the water tanks and external supply networks bad condition, are usually responsible. It is important to note that the number of total coliforms found in samples from the water tanks decreased. In a large number of water samples coming from the water tanks, one or two total coliforms are found and are estimated as undrinkable samples although they are not heavily infected. The internal supply network has lower undrinkable percentage from the water tanks because the chlorination is often applied at the water tank exit.

2004

Sum Undrinkable Undrinkable Sum Undrinkable Undrinkable Sum Undrinkable Undrinkable percentage percentage percentage

Parameters Nitrate Total coliform 100 mL

83

4
13

149 11
143 9

7
6

376
394

15
99

4
25

Ammonium 107 14

98 39

40

196 89

45

399 125

31

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4. Conclusions (a) The water quality depends on its chemical and microbiological condition. The alteration of the chemical parameters of a water system used as potable water, especially when it is underground, depends on many parameters like the solubility of pollutants, their adsorption and halflife, from the climatic and hydrogeological conditions, mainly the percolation factor, the underground flow velocity of water, the slope and composition of the formations, the aquifers level [17,18]. At the study area the majority of the drinkable water analyzed samples come from deep drills passing from cohesive formations accordingly to geological maps and studies implemented in the area and therefore chemical composition relatively stable and generally not influenced from agricultural activities was observed. (b) In the areas with penetrable formations and agricultural activity, the nitrates presence was observed in relatively stable concentrations (Fig. 1) in time, because of their high mobility in soil [19]. About 5.7% of tested samples in the County of Kozani contained NO3-N at concentrations greater than 50 mg/L and lower than 210 mg/L. In Europe there are evidences that 87% of the agricultural areas have nitrate concentrations in groundwater above 25 mg/L and 22% above 50 mg/L [20]. In USA ground water accounts for 86% of their total water resources and provides 24 and 95% of the drinking water supply for urban and rural areas, respectively. About 6.4% of tested wells in the USA contained NO3-N at concentrations greater than 10 mg/L and 13.2% contained 3.110 mg/L. In Greece 70% of the total consumed water is used for irritating activities, 10% for drinking and 20% for industrial use.The nitrate problem of groundwater in Greece is not clear [21].

(c) The water is easily microbiologically infected in the supply sources because of their insufficient sanitary protection and the external network bad condition. For this reason the continuous and systematic chlorination and microbiological monitoring of the drinking water is essential. (d) The authorities responsible for the water supply have to take the proper measures for the protection of springs and drills, the maintenance and cleaning of water networks and tanks, as well as informing and training the authorised personnel in the correct application of chlorination and in monitoring the condition of springs, drills, water tanks, and water supply networks in their areas. (e) The condition of the water tanks, which are often old, not correctly situated, wrongly constructed, inefficiently maintained and not systematic chlorinated, contributes considerably to the downgrading of the water quality. (f) The condition of the water supply networks is a factor which contributes as much as the water tanks to the downgrading of the water quality, often due to their age, leaks, wrong placement near the wastewater network, absorption problems because of water cuts, etc. References
[1] Directive 2000/60/EK, Establishing a Framework for Community Action in the Field of Water Policy. Law 3199/2003 (EK 280A/9-12-2003), Protection and Management of Water, in accordance to the Directive 2000/60/EK. KYA Y2/2600/2001 (EK 892B/11-7-2001), Quality of Water Used for Human Consumption, in accordance to the Directive 98/83/EK of the Council of the European Union. Law Y2/4052/8-11-2000, Systematic Control and Monitoring of Drinking Water for the Protection of Public Health.

[2]

[3]

[4]

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[15] M. Manassis, in: Tziola (Ed.), Quality Characteristics and Treatment of Water, Thessaloniki, 2001. [16] A.R. Corbitt, Standard Handbook of Environmental Engineering, 2nd edn., McGraw-Hill Handbooks, NY, 1999. [17] G. Kallergis, Applied-Environmental Hydrogeology I, 2nd edn., Technical Chamber of Greece, Athens, 2001, pp. 3344. [18] G. Soulios, General Hydrogeology I, University Studio Press, Thessaloniki, 1986, pp. 4145. [19] G.S. Vasilikiotis and K.K. Fytianos, in: Ziti (Ed.), Methods of Environmental Control Pollution, Thessaloniki, 1986, pp. 7879. [20] V.Z. Antonopoulos and S.E. Tsiouris, Evaluation of nitrate groundwater pollution using leaching indices and environmental implications, in: Proc. of International Conference of Xanthi, Vol. I, pp. 5157. [21] P. Latinopoulos, The problem of groundwater nitrate contamination and its control in the European Union, in: Proc. of Helleco 99 Conference, Technical Chamber of Greece, Thessaliniki, 1999, p. 256.

[5] Law A5/288/86, Drinking Water Quality, in accordance to the Directive 80/778/EOK. [6] Directive 80/778/EOK, Drinking Water Quality. [7] Directive 98/83/EK, Quality of Fresh Water Used for Human Consumption. [8] APHA, Standard Methods for the Examination of Water and Wastewater, 20th edn., APHA, AWWA, WPCF, Washington, DC, 1992. [9] ISO 5667, Water Quality Sampling Part 2 Guidance on Sampling Techniques. [10] ISO 9308-1, Water Quality Detection and Enumeration of E. coli and coliform bacteria. [11] ISO 7899.02, Water Quality Detection and Enumeration of Intestinal Enterococci. [12] ISO 6222, Water Quality Enumeration of Culturable Micro-organisms Colony Count by Inoculation in a Nutrient Agar Culture Medium. [13] US Food and Drug Administration, Bacteriological Analytical Manual, 2001, www.cfsan.fda.gov. [14] ISO 17025, General Requirements for the Competence of Testing and Calibration Laboratories.

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