TITLE …………………… 29 Journal homepage: www.fia.usv.ro/fiajournal Journal of Faculty of Food Engineering, Ştefan cel Mare University of Suceava, Romania Volume XV, Issue 1- 2016, pag. 29 - 35 CHEMICAL ANALYSIS OF FRESH WATER FROM A KARST AREA IN UKRAINE * Volodymyr Diychuk 1 , Anastasiya SACHKO 1, Igor WINKLER 1,2 1Department of Chemical Analysis, Food Safety and Testing, Institute of Biology, Chemistry and Bioresources, Yu. Fedkovych National University of Chernivtsi, 2 Kotsyubynsky St., Chernivtsi, 58012, Ukraine v.diychuk@chnu.edu.ua 2Department of Medicinal Chemistry, Bucovina State Medical University, 2 Teatralna Sq., Chernivtsi, 58002, Ukraine i.winkler@chnu.edu.ua *Corresponding author Received January 26th 2016, accepted March 24th 2016 Abstract: The chemical composition analysis was performed for fresh water samples taken from a karst area located in the region of Chernivtsi, Ukraine. Water samples were taken from private wells, springs and open ponds near Verenchanka. Total water hardness exceeded the sanitary limits for all the well samples and ranged from 11 to 29 mmol-eq/l (respective sanitary limit is 7 mmol-eq/l). This can be caused by the close-to-surface karst formations located under the village which release mas- sive amounts of water hardness ions in the well water as a result of karst ablation. However, the heavy metals content (Fe, Zn, Cu, Mn) was within the sanitary limits excepting two samples which slightly exceeded zinc content. Total hardness of the surface spring and pond waters ranged from 6.2 to 11 mmol-eq/l and the heavy metals ions contents were comparatively low. Keywords: fresh water, total hardness, heavy metals content, karst area, trilonometry, atom- absorption spectrometry. 1. Introduction Availability of fresh water is a key issue for any inhabitant of municipal or rural ar- eas and it is an indicative parameter of the life quality and safety, keeping the public health and improvement of the life condi- tions. This problem has gained the primary importance for many countries and regions all over the world. It is known that quality of approximately 10 % of the drinking water in Ukraine re- mains below sanitary standards and re- quirements set for its chemical composi- tion and bacterial parameters [1]. Moreo- ver, a lot of inhabitants of rural areas of Ukraine traditionally consume the untreat- ed water, which is often contaminated by chemical and/or germ agents, which results in worsening of the total organism re- sistance and immune status [2]. It seems interesting to investigate possible effects of the karst formation and devel- opment processes on the drinking water quality in the nearby areas. Karst is an integral watercycling rock ge- osystem enriched with numerous pores and channels formed as a result of dissolu- tion/sedimentation of the primary rock ma- terials by circulating natural waters. The near-surface subterranean karst formation causes numerous specific phenomena in the local relief and hydrology related to significant voidage and channels penetra- bility of the rock. All these factors result in formation of some specific karst land- http://www.fia.usv.ro/fiajournal mailto:v.diychuk@chnu.edu.ua mailto:i.winkler@chnu.edu.ua Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - Suceava Volume XV, Issue 1 – 2016 Volodymyr DIYCHUK, Anastasia SACHKO, Igor WINKLER, Chemical analysis of the freshwater from a Karst area in Ukraine, Food and Environment Safety, Volume XV, Issue 1 – 2016, pag. 29 – 35 30 scapes. Changes in the hydrology regime of the area can lead to dynamic changes in the karst character, which causes changes in the water cycling followed by possible changes in the local natural waters compo- sition [3]. Fig. 1. Approximate location of vil. Verenchanka in Chernivtsi region (encircled) and the same in bigger scale (arrowed) in the map of the West of Ukraine (embedded). The karst rocks can perform a strong ad- sorption action since they are formed by quite porous materials capable to extract various heavy metals while water is infil- trating through karst. On the other hand, the karst rocks is represented mainly by a comparatively easy-soluble limestone and gypsum, which results in releasing of sig- nificant amounts of calcium and magnesi- um (hydro)carbonates, sulfates and other salts into water. As a result, the overall influence of the karst rocks on the drinking water quality and composition depends on numerous lo- cal specifics and should be investigated thoroughly for each locality of interest. The village of Verenchanka is located in Zastavna district of Chernivtsi region, Ukraine (see Fig. 1) at the well-known subsurface gypsum karst formation. Nu- merous occurrences of karst phenomena have been continuously reported in the nearby area and within the village. Be- sides, there is a gypsum opencast mine near Verenchanka. The 20-30 meters thick sub-surface karst formations are mostly responsible for the active karst manifestations in the middle part of Pruth-Dnister interfluve. Local karst manifestations in the area of Ve- renchaka are related to the block tectonic structure of the local rock and different karst opening depth by the draining rivers incuts [4]. Therefore, it is expected that karst phe- nomena can provide quite a tangible influ- ence on the well-water quality in the vil- lage. Basing on this assumption we Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - Suceava Volume XV, Issue 1 – 2016 Volodymyr DIYCHUK, Anastasia SACHKO, Igor WINKLER, Chemical analysis of the freshwater from a Karst area in Ukraine, Food and Environment Safety, Volume XV, Issue 1 – 2016, pag. 29 – 35 31 planned and carried out a systematic inves- tigation of some physico-chemical parame- ters of the water samples taken from vari- ous sources inside and around the village. Water quality parameters have been deter- mined using the following methods: or- ganoleptic evaluation (taste, odor and col- or), trilonometric determination of the total water hardness and atom-absorption spec- trometry (AAS) measurement of some heavy metals contents. 2. Materials and methods Water sampling has been performed ac- cording to [5, 6] using the 0.5 liter poly- ethylene containers washed preliminary with nitric acid and then distilled water. 5 ml of the highly purified nitric acid have been added to each water sample for the purpose of conservation. Total series in- volved 32 samples taken from the wells, springs and ponds inside and nearby the vil. Verenchanka. Total water hardness has been determined using the well-known method of trilo- nometry based on formation of stable complexes of ethylenediamine tetraacetic acid (EDTA) with Ca2+ and Mg2+ ions. pH of the solution was kept at 9–10 by the ammonia buffer solution (NH4Cl + NH4OH) and Eriochrome Black-T was used as an indicator. Then the heavy metals content has been measured by AAS. It should be noted that this method has proved its superior sensi- tivity, high accuracy and requires compara- tively short time. On the other hand, it re- quires preliminary chemical decomposition of the samples. The ‘matrix’ composition should also be taken into consideration. Qualitative determination of Fe, Zn, Mn and Cu in all the samples has been done according to the method [7, 8] using the air-acetylene flame and standard solutions approach. Details of the determination re- gimes for different elements are available from Table 1. Table 1. Determination regimes for Fe, Zn, Mn and Cu Element Wavelength, nm Determination limit, mg/l Fe 248.3 0.08 Zn 213.9 0.012 Mn 279.5 0.025 Cu 324.8 0.04 3. Results and discussion As seen from a map (see Fig. 2), the wells are scattered practically all around the vil- lage area. They are located both in valleys and uplands. The valley wells are relatively shallow (7, 8, 20, 21 and 28) and their depth is limited by 9 meters while the up- land wells (1, 13÷19, 22÷27, 29÷32) are much deeper and their depth can reach 25 m (see Table 2). An average well depth in the area is 12.9 m. As seen from Table 2, the water quality parameters are ranged within quite wide limits. However, no reliable dependence between well locations and the water quali- ty parameters has been found. In our opin- ion, this can be caused by different geolog- ical conditions and water feeding regimes for each of the wells. Our results are in good agreement with a concept of geologi- cal structure of the region. Therefore, high total hardness can be caused by an intense circulation of the well-feeding waters in- side the Miocene gypsum rocks forming karst structures in the area. The total water hardness was found very high for all the wells and it exceeds substantially the sani- tary value. More detailed results of the wa- ter quality investigation and explanation of the sampling points location are given in Table 3. Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - Suceava Volume XV, Issue 1 – 2016 Volodymyr DIYCHUK, Anastasia SACHKO, Igor WINKLER, Chemical analysis of the freshwater from a Karst area in Ukraine, Food and Environment Safety, Volume XV, Issue 1 – 2016, pag. 29 – 35 32 Table 2. Well parameters in the area of vil. Verenchanka № Parameter Averaged value Minimal val- ue Maximum val- ue Permissible sanitary values 1 Total hardness, mmol-eq/l 18.52 11 29 7 2 Fe content, mg/l < 0.08 < 0.08 0.09 0.3 3 Zn content, mg/l 0.38 0.082 1.887 1.0 4 Cu content, mg/l 0.031 0 0.265 1.0 5 Mn content, mg/l < 0.02 < 0.02 < 0.02 0.1 6 Well depth, m 12.875 7 25 – Fig. 2. Locations and total hardness of the water sampling points It is known that calcium and magnesium sulfates, chlorides, carbonates, bicar- bonates and other soluble forms are re- sponsible for the natural water hardness. Soft water is conditionally limited by the total hardness 3.5 mmol-eq/l; moderately hard – by 7; hard – by 10, and very hard water is over 10 mmol-eq/l. It should be understood, that this classification is based mostly on the organoleptic characteristics since water tastes bitter if it is excessively hard. Therefore, it is desirable to have drinking water of the soft or moderately hard category. It was found that the 10 well (7, 15, 16, 20, 21, 25, 29÷32) water samples had water hardness higher than the averaged value (18.52 mmol-eq/l). They are scattered all over the village but part of them are locat- ed as a group (16, 25, 30, 31, 32). Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - Suceava Volume XV, Issue 1 – 2016 Volodymyr DIYCHUK, Anastasia SACHKO, Igor WINKLER, Chemical analysis of the freshwater from a Karst area in Ukraine, Food and Environment Safety, Volume XV, Issue 1 – 2016, pag. 29 – 35 33 Table 3. Complete results of analysis of the water samples Sample Content, mg/l Total hardness, mmol- eq/l Organoleptic parameters Well depth Type of the sampling point Fe Mn Zn Cu Smell, points Taste, points and character Colour 1 – – 0.11 0.065 18 1 1, bitter-sour no 15 well 2 – – 0.016 – 6.2 2 – yellowish – pond 3 – – 0 – 11.4 1 0 no – spring 4 – – 0.021 0.025 15.6 1 1, bitter-sour no 25 well 5 – – 0.02 – 6.2 2 1 yellowish – pond 6 – – 0.031 0.035 9 1 1 no – spring 7 – – 0.082 – 26 1 2 bitter-sour no 7 well 8 – – 0.143 0.015 17 1 0 no 8 well 9 – – 0.094 0.02 16.4 1 1, bitter-sour no 20 well 10 – – 0.032 0.025 10 1 – no – spring 11 0.16 – 0.064 0.015 10 1 – yellowish – pond 12 0.08 – 0.055 0.015 7 1 – no – spring 13 0.08 – 0.106 – 11 1 0 no 12 well 14 – – 0.134 – 11 1 0 no 15 well 15 – – 0.196 – 22 1 1, bitter-sour no 15 well 16 – – 0.137 – 22 1 1, bitter-sour no 20 well 17 – – 0.746 0.015 18 1 1, bitter-sour no 15 well 18 – – 0.097 0.01 14 1 0 no 12 well 19 – – 0.111 0.04 15 1 1, bitter-sour no 12 well 20 0.09 – 0.941 0.265 26 1 2 bitter-sour no 9 well 21 0.08 – 0.143 0.02 24 1 2 bitter-sour no 8 well 22 – – 0.144 0.045 14 1 0 no 12 well 23 0 – 0.805 – 14 1 1 no 12 well 24 0.08 – 0.281 0.035 14 1 1 no 15 well 25 – – 0.159 0.02 21 1 2 bitter-sour no 15 well 26 – – 0.179 0.035 16 1 1, bitter-sour no 12 well 27 – – 1.887 – 13 1 1 no 15 well 28 – – 1.379 0.01 12 1 1 no 7 well 29 – – 0.3 0.045 29 1 2 bitter-sour no 12 well 30 – – 0.214 0.025 20 1 1, bitter-sour no 12 well 31 – – 0.263 0.025 23 1 1, bitter-sour no 14 well 32 0.08 – 0.48 0.065 28 1 2 bitter-sour no 15 well Concentration of Zn is another particular local feature, which even exceeded the san- itary value in some wells. The highest Zn contents have been found in the samples number 17 (0.745 mg/l), 20 (0.941 mg/l), 23 (0.805 mg/l), 27 (1.887 mg/l – exceed- ing) and 28 (1.379 mg/l – exceeding). In the contrary, the concentration of Cu is within the sanitary values for all the sam- ples. The concentration of Fe was also far Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - Suceava Volume XV, Issue 1 – 2016 Volodymyr DIYCHUK, Anastasia SACHKO, Igor WINKLER, Chemical analysis of the freshwater from a Karst area in Ukraine, Food and Environment Safety, Volume XV, Issue 1 – 2016, pag. 29 – 35 34 below its sanitary limits. No correlation between the total hardness and concentra- tions of the heavy metals ions has been es- tablished for all the wells except the well 20. This sample has showed both high total hardness (26 mmol-eq/l) and quite high contents of Fe, Zn and Cu (0.09, 0.941 and 0.265 mg/l respectively). This well is lo- cated quite close to the area of the former spirits production factory that has been closed because of the karst activation in the nearby area years ago. In our opinion, for- mer and continuous spills and discharges of the factory’s technological liquids and wastewaters could be accumulated in the local soil and caused high contents of the salts in this sample. Spring and pond waters analysis results There are some springs and ponds within the village and the organoleptic and physi- co-chemical parameters of their waters have also been analyzed in the same man- ner as for the wells in order to enhance our survey of natural water quality in the area. As seen from comparison of the analysis results, the spring and pond water compo- sition is quite different from that of the well water (see Fig. 3). For instance, the total hardness of the spring and pond water sample is ranged within 6.2-11 mmol-eq/l while this parameter for the well water samples is significantly higher – its mini- mal value for the well waters is 11 mmol- eq/l. This is an evidence of difference in water feeding sources of local wells and springs/ponds. The wells are fed mostly from the underground water sources, which seem to be enriched with Ca and Mg salts. It is quite obvious since the region is located on the thick and comparatively high (6-22 m from the surface) bed of gyp- sum [9-11]. This is the most probable source of the water hardness ions released to the well waters. Alternatively, the sur- face springs and ponds are fed mostly by the rain and snowmelt waters, which are much softer. 0 2 4 6 8 10 12 1211106532 sample Total water hardness, mmol/L Fig. 3. Total hardness of the spring and pond water samples 0.00 0.03 0.06 0.09 0.12 0.15 mg/L Fe Zn Cu 1211106532 sample Fig. 4. Contents of the heavy metals ions (Fe, Zn, Cu) in the spring and well waters. More detailed results of investigation of the heavy metals ions in the spring and pond waters are represented in Fig. 4. As seen from this Figure, the samples 11 and 12 have the highest Fe (0.16 and 0.08 mg/l respectively) and Zn (0.064 and 0.055 mg/l) contents. However, even these values are far below their sanitary levels. 4. Conclusion The well water of village Verenchanka has shown comparatively high total hardness (11-29 mmol-eq/l), which exceeds signifi- cantly the sanitary limits. This problem can Food and Environment Safety - Journal of Faculty of Food Engineering, Ştefan cel Mare University - Suceava Volume XV, Issue 1 – 2016 Volodymyr DIYCHUK, Anastasia SACHKO, Igor WINKLER, Chemical analysis of the freshwater from a Karst area in Ukraine, Food and Environment Safety, Volume XV, Issue 1 – 2016, pag. 29 – 35 35 be originated from the thick and close-to- surface karst formations in the village area. According to the AAS results, the sub- threshold or exceeding contents of Zn have been registered in the samples 17, 23, 27 and 28 (0.746, 0.941, 0.805 and 1.887 mg/l respectively). The highest Zn content in the sample 28 that exceeds the sanitary limits can be resulted by the influence of the old spirit production factory spills and wastewater discharges that took place in the nearby area. Concentrations of Fe, Mn and Cu in all the samples were far below the sanitary limits. On the other hand, the total hardness of the surface water objects (springs and ponds) in the area of investi- gation was found much lower than that of the well water. This hardness was ranged within 6.2-11 mmol-eq/l and, in our opin- ion, this is an evidence of different water feeding sources for the surface water ob- jects and the wells. The former are fed pre- liminary by the softer rain and snowmelt water while the latter are fed by the karst- originated hard ground water. Concentra- tions of Fe, Zn, Mn and Cu in all the sur- face samples were also much lower than the sanitary limits. Taking into account the character of the well water feeding in the area of investigation, no solution can be proposed to bring the total water hardness back to its sanitary limits except intense utilization of water softener agents when- ever this parameter seems critical (cook- ing, washing, using water in the home heating systems network). Karst area is much wider than the area of the village and finding a spot to establish a soft water source near the village does not seem real- istic. On the other hand, the surface water springs can provide water with appropriate hardness but they cannot cover required water output while soft water from the lo- cal ponds can hardly meet other sanitary requirements (mostly bacteriological). 5. References [1]. A Law of Ukraine “About Drinking Water and Water Supply”. Supreme Council of Ukraine: Official Edition. 36 p. Kyiv, (2005). (In Ukrainian). [2]. VOLOSHKINA O. S., Yakovlev E. O., UDOD V. M., To environmental safety of surface water bodies. Council of National Security and De- fense of Ukraine, Institute for National Security problems: Official Edition. 139 p. Kyiv, (2007). (In Ukrainian). [3]. KLIMCHOUK A. B., Subsidence hazards in different types of karst: Evolutionary and speleoge- netic approach. Envir. Geol., 48(3): 287-296, (2005). [4]. RIDUSH B., Technogenic karst activization in Zastavna karst area. Sci. Bull. of ChNU (Geogra- phy), 395: 189-196, (2006). (In Ukrainian). [5]. SHARMAL B., TYAGI S., Simplification of Metal Ion Analysis in Fresh Water Samples by Atomic Absorption Spectroscopy for Laboratory Students. J. Lab. Chem. Edu., 1(3): 54-58, (2013). [6]. BADER N. R., Sample preparation for flame atomic absorption spectroscopy: an overview. RA- SAYAN J. Chem., 4(1): 49-55, (2011). [7]. WELZ B., SPERLING M., Atomic Absorption Spectrometry, Wiley-VCH, Weinheim, Germany, 941 p., (1999) [8]. RAMADAN N., BADER, N. R., ZIMMER- MANN B., Sample preparation for atomic spectro- scopic analysis: an overview. Adv. in App. Sci. Res., 3(3): 1733-1737, (2012). [9]. KLIMCHUK L. M., Information bulletin on activization of dangerous exogenic geological pro- cesses in Ukraine according to EGP monitoring data. Geoinformation of Ukraine. 4: 22p, (2007). [10]. KLIMCHOUK A. B., Hypogenic speleogene- sis, its hydrogeological importance and role in the karst evolution, DIAIPI, Simferopol, 411 p., (2013) (In Russian). [11]. KLIMCHOUK A. B., TOKAREV S. V., Problems of drinking water sources protection at the karst exposure. Ukr. J. Geogr. 1: 43-52 (2014) (In Russian). 1. Introduction 4. Conclusion