Journal of Environmental Protection and Ecology 8, No 4, 950–955 (2007) Environmental legislation
REVIEW OF BACTERIOLOGICAL AND PHYSICOCHEMICAL QUALITY OF natural mineral WATER PRODUCED IN THE REPUBLIC OF MACEDONIA M. Kochubovski*, B. Aleksoski, V. KENDROVSKI, M. DIMOVSKA Republic Institute for Health Protection, 6 ‘50 Divizija’ Street, 1000 Skopje, Republic of Macedonia E-mail:
[email protected] Abstract. Republic of Macedonia as a candidate country to the European Union has a goal to harmonise its national legislation related to the environmental protection. One of the achieved goals is Final Draft of a new Book of rules for Natural Mineral Water and Mineralised Water Safety. The new Book of Rules applies to natural mineral waters in accordance with the Council Directives 80/777/EEC, 96/70/EEC and 2003/40/EC, but does not apply to waters which are medicinal products within the meaning of Council Directive 65/65/EEC. WHO recommendations (Guidelines for drinking water quality, 3rd ed., Copenhagen, 2004) are also included in the new Book of Rules. Codex Alimentarius Commission, Vol.XII/1987 and revision 1997 – Methods of Analysis and Sampling, Vol.XIII/1994 and Vol.XII/2001 – Codex Standards for Natural Mineral Waters as well the local circumstances and priorities have been taken into consideration. From the 1st January till the 20th December 2005 were examined 235 samples of 17 different types of bottled natural mineral water produced in the Republic of Macedonia, in the laboratories of the Republic Institute for Health Protection – Skopje. 187 samples of natural mineral water have been taken by the Republic Institute for Health Protection – Skopje according to its own plan for monitoring. Food Directorate has sent 4 samples, and 44 samples of natural mineral water have been taken on the request of the Local Producers. From the examined natural mineral water have been found: 13 samples have been improper because of higher content of nitrites (5.7%), 1 sample up to increased level of nickel, 1 sample up to increased level of chloride, 1 sample because of higher level of strontium, 1 sample up to increased level of phosphate, 3 samples because of higher COD (1.3 %), and 15 samples because of bacteriological contamination (6.6%). As a result of incomplete declaration 2 samples of natural mineral water have been found as improper. For the above investigation have been used the EU Directives and related Code Alimentarius Standards in order to have harmonised limit values for the parameters of interest. In this paper are presented only the results of physicochemical and bacteriological investigations. Keywords: natural mineral water, EU legislation, Codex Alimentarius Standards.
AIMS AND BACKGROUND Natural mineral waters have been used for drinking and healing long time ago. Underground waters basing on their own mineralisation, chemical and gaseous properties, content of radionuclides, are different from ordinary drinking water (low mineralised waters). *
For correspondence.
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Natural mineral water is water with content of 1000 mg/l dry residues1. Natural mineral waters are also water with more than 250 mg/l dry residues and are called oligo-mineral natural mineral waters. They are obtained directly from natural or drilled sources from underground water bearing strata2. In the nature there is various numbers of natural mineral waters that can be classified by mineralisation, ion and gases content, level of trace elements, radionuclides, pH, etc. Ivanov and Nevraev (1964, Rev. 1977), have made genetic classification of natural mineral waters based on ionic content can be accomplished a picture about hydrochemical conditions, balneological aspects, and their curative properties by drinking, or bathing into. Regarding their mineralisation natural mineral waters are classified in 4 groups: 1. Waters with higher mineralisation compared to ordinary drinking water (1-5 g/l) with similar effects like ordinary drinking water. 2. Waters with medium mineralisation (5-15 g/l), most convenient in balneology. 3. Waters with high mineralisation (15-35 g/l), mostly for healing by bathing. 4. Brine waters (35-150 g/l), only for bathing. Based on geological-tectonic development, complex structural-geological content, volcanic activities, etc., on the territory of the Republic of Macedonia there are several sources of natural mineral waters3. With examination of natural mineral waters have been occupied small number of experts in the past, but nowadays the interest for investigation and exploitation of them is very much increased. On the territory of the Republic of Macedonia mostly presented are natural mineral waters with 1-3 g/l mineralisation (Table 1). Table 1. Survey of natural mineral waters according to their mineralisation
Total number of natural mineral waters occurrence in Tectonic units in the Republic the Republic of Macedonia, according to their mineralisation (g/l) of Macedonia 5g Serbian-Macedonian massive 4 13 – – Vardar’ zone 4 62 10 3 Pelagonia’s massive 5 25 6 2 West-Macedonian zone 6 18 9 3 Total 19 118 25 8
Most of the natural mineral waters in the Republic of Macedonia are with pH 7-8. Most of natural mineral waters are hydro-carbonate with various cationic content (Table 2).
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Table 2. Survey of natural mineral waters according to their ionic content
Occurrences of natural mineral waters in tectonic units of the Republic of Macedonia Type of water according to Serbianthe ion content Vardar’ Pelagonia’ West-Mac. Mac. maszone massive zone sive Hydro-carbonate with vari 1 36 9 24 ous cationic content Hydro-carbonate-sodium 3 2 1 – Hydro-carbonate-chloride, 9 13 16 5 sodium and calcium-sodium Hydro-carbonate-sulphate with 2 12 – 1 various cationic content Sulphate, with various cati 1 – – 1 onic content Sulphate-chloride with vari– 6 2 2 ous cationic content Sulphate-hydro-carbonate 1 8 5 3 chloride with various cationic content Chloride-sodium – 2 5 – Total 17 79 38 36
Total 70 6 43 15 2 10 17 7 170
In part of the natural mineral waters on the territory of the Republic of Macedonia, have been noticed a chemically inert gaseous elements occurring in small amount like argon (Ar), krypton (Kr), xenon (Xe), neon (Ne), helium (He), etc. Upon the above mentioned could be concluded that on the territory of the country there are many natural mineral waters with various ionic and gaseous content as well with different temperature, which could be expected respectively regarding the terrain configuration, geological-tectonic structure, and various hydro-geological conditions3. In the natural mineral waters there are also trace elements. Their content is less than 10 µg/l, except in the case of bromine and iodine. Nevertheless the small content of trace elements, their role is very important for human body4. experimental The examination of natural mineral waters has been done in accordance with Council Directive 80/777/EEC, 96/70/EEC and 2003/40/EC (Ref. 5), Codex Alimentarius Commission (Ref. 6) as well WHO recommendations (Ref. 7). From 1st January till 20th December 2005 were examined 235 samples of 17 different types of bottled natural mineral water produced in the Republic of 952
Macedonia, in the laboratories of the Republic Institute for Health Protection – Skopje. Results The examination of natural mineral waters has been done in accordance with Council Directive 80/777/EEC, 96/70/EEC and 2003/40/EC, WHO recommendations (Guidelines for Drinking Water Quality), and Codex Alimentarius Commission, Vol. XII/1987 and revision 1997 – Methods of Analysis and Sampling, Vol. XIII/1994 and Vol. XII/2001 – Codex Standards for Natural Mineral Waters, as well the local circumstances and priorities have been taken into consideration1. The results from the examination of natural mineral water samples show that: 13 samples have been improper due to higher content of nitrites (5.7%), i. e. 1 sample – increased level of nickel, 1 sample – increased level of chloride, 1 sample – higher level of strontium, 1 sample – increased level of phosphate, 3 samples – higher COD (1.3 %), and 15 samples – of bacteriological contamination (6.6%). As a result of incomplete declaration 2 samples of natural mineral water have been found as improper (Tables 3 and 4). Table 3. Annual review of the analysed samples of natural mineral waters produced in the Republic of Macedonia in 2005
Name of natural Sampled on Sampled on Sampled on Total number Number of mineral water request of request of request of of the anaimproper RIHP Food’s Direc- producers lysed samples samples torate Pelisterka 26 2 1 29 – Kozuvcanka 28 1 – 29 11 Bonakva 7 1 20 28 – Dobra Voda 14 – 5 19 3 Akva Vita 20 – 2 22 7 Badarijan 2 – 3 5 – Bo’ica 2 – – 2 – Germina 11 – 1 12 2 Gorska 12 – 3 15 – Davina 6 – – 6 4 Ilina 13 – 2 15 – Inakva 13 – 1 14 4 Heraklea 13 – – 13 1 Total
167
4
38
209
30
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Table 4. Annual review of the analysed samples of natural mineral waters produced in the Republic of Macedonia in 2005, without Contract with RIHP*
Name of natural Sampled on Sampled on Sampled on Total number Number of mineral water request of request of request of of the anaimproper RIHP Food’s Direc- producers lysed samples samples torate Bistra 5 – 2 7 1 Krapjanka 2 – – 2 1 Menada 7 – 4 11 – Pela Rosa 6 – – 6 – Total 20 – 6 26 2 * RIHP – Republic Institute for Health Protection – Skopje.
Expert opinion has been performed by the Republic Institute for Health Protection according to the international and domestic legislative. In the world there is an increasing consumption of natural mineral waters, as well in our country. In Macedonia there are several big sources of natural mineral waters, especially in the area of v. Medjitlija – Bitola (on the south, near the Macedonian-Greek border), v. Volkovo – Skopje, Katlanovo, v. Proevci – Kumanovo, etc. All these waters are approved by the Food’s Directorate. According to the pH level, natural mineral waters are grouped as acid – Pelisterka (6.01), Kumanovka (6.01), Pela Rosa (6.3) and Badarian (6.3); alkalic – Davina (7.5). The rest of them (more than 20) natural mineral waters, and 3 mineralised waters are with neutral pH. Natural mineral waters according to their mineral anionic and cationic content are grouped in: calcium-magnesium (Pelisterka, Badarian, Ilina and Katlanovski Biser), magnesium (Skopjanka, Katlanovka and Davina), fluoride (Badarian), calcium (Dobra Voda and Kumanovka), sodium (Davina and Vineam mineralised water), potassium (Kumanovka, Katlanovka, Menada, Car Samuil and Dobra Voda) and sulphate (Car Samuil, Davina, Kumanovka, Katlanovka and Negorcanka). All natural mineral waters contain bicarbonates in the range of 70.6-2125 mg/l. According to the minerals content, most of natural mineral waters are with calcium > 200 mg/l, magnesium > 50 mg/l, fluorides > 1 mg/l, chloride and sulphate > 200 mg/l, sodium > 150 mg/l, potassium > 12 mg/l. In the group of oligo-mineral waters are Menada, Kozuvski Biser and Negorcanka, with less than 1 g/l of dry residues8. Natural mineral waters – Skopjanka in 1967 and Kumanovka in 1973 – have got Certificate for balneological assessment from the Institute for Internal Diseases, Department for Balneology – Belgrade, Yugoslavia. Natural mineral water Pelisterka has got such a Certificate for balneological assessment from the Institute for Health Protection, Slovenia in 1968. 954
According to the range of anions and cations as well as pH, especially should be mentioned the quality of the mineral waters Pelisterka, Kozufcanka, Badarian and Ilina. The mineral waters Ilina and Kozufcanka have got a Certificate for balneological assessment of natural mineral waters by the National Center for Balneology and Rehabilitation in Sofia, Bulgaria, in 1999. CONCLUSIONS From the above mentioned can be concluded that in the world and in our country there is a continuous trend of increasing of consumption of natural mineral waters. In Macedonia there are several big sources of natural mineral waters, especially in the area of v. Medjitlija – Bitola (on the south, near the Macedonian-Greek border), v. Volkovo – Skopje, Katlanovo, v. Proevci – Kumanovo, etc. All these waters are approved by the Food’s Directorate. All bottled natural mineral waters produced in the Republic fulfill the conditions of related standards of the EU Directives and Codex Alimentarius. According to the range of anions and cations as well as pH, especially should be mentioned the quality of the mineral waters Pelisterka, Kozufcanka, Badarian and Ilina. references 1. Book of Rule for Natural Mineral Waters. Official Gazette of SRM No 58/78, Skopje, 1978. 2. FAO/WHO: Codex Alimentarius Commission. Vol. XII. Codex Standards for Natural Mineral Waters 108-1981, Rev. 1-11/97, amended in 2001. 3. G. Kotevski: Hydrogeology of Natural Mineral, Thermal and Thermal-mineral Waters on the Territory of SRM. Skopje, 1987. 4. M. Komatina: Medical Geology. Belgrade, 2001. 5. Commission Directive 2003/40/EC: Establishing the List, Concentration Limits and Labeling Requirements for the Constituents of Natural Mineral Waters and the Conditions for Using Ozone-enriched Air for the Treatment of Natural Mineral Waters and Spring Waters. Brussels, 2003, 34-39. 6. FAO/WHO: Codex Alimentarius Commission. Vol. XII. Codex Standards for Natural Mineral Waters 108-1981, Rev. 1-11/97, amended in 2001. 7. WHO: Guidelines for Drinking Water Quality. 3rd ed. Recommendations, Vol. 1, Geneva, 2004. 8. M. Kochubovski, P. Filjanski, D. Gjorgjev, D. Velev, L. Kolevska: New Standards of FAO/WHO for Quality of Natural Mineral Waters. In: Proc. of XXIII October’s Meetings of Medical Laboratory and Sanitary Technicians of the RM, Ohrid, 1995, 65-66. Received 11 April 2006 Revised 10 June 2006
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