This paper describes research on two of the largest karst springs in Poland's Tatra Mountains – Goryczkowe and Bystrej Górne – both located in the Tatra National Park. The aim of the study was to determine the potential contributing area for the Bystrej Gorne Spring. Research has shown that seasonal changes in the physical and chemical properties of water in both springs followed a similar pattern; however, observed differences were not statistically significant. Additionally, research has shown that the potential contributing area is different than that previously identified by other researchers. The chemical composition of water obtained from each spring was dominated by Ca2+ and HCO3, and included small amounts of the biogenic NO3 ion. The highest values of the measured physical and chemical parameters were noted in winter, while the lowest values were noted in spring and summer. Principal component analysis was used to assess the physical and chemical parameters of water obtained from both studied springs. Water dilution and catchment biological activity were identified as two key processes affecting physical and chemical properties of karst spring water. Several differences were identified between the springs – water temperature, pH, mineralization, as well as the concentration of Mg2+, HCO3, and SO24.

INTRODUCTION

Springs are natural outflows of groundwater on the Earth's surface. High discharge springs are of particular importance and supply a significant percentage of drinking water in the world (Veni et al. 2001). Ford & Williams (2007) estimate that about 25% of the world's population uses water obtained from karst aquifers every day. Most karst springs occur in areas characterized by unique hydrogeological conditions, where surface water systems and groundwater systems are closely linked and form one water circulation system (White 1993). Vaucluse springs are one type of karst springs that yield autochthonous water, with mean discharge at more than 100 L s−1 (Barczyk 2008).

Vaucluse spring waters originate in extensive systems of karst fissures, which make the identification of contributing areas difficult. Therefore, hydrologists and hydrogeologists studying karst aquifers often analyze water chemistry as well as selected physical properties of water. Changes in physical and chemical properties of water are used to identify areas contributing groundwater, assess water flow rates, and compare groundwater data for different geographic regions (Shuster & White 1971; Cowell & Ford 1983; Scanlon & Thrailkill 1987; Taylor & Greene 2008). Examples of the types of data usually sought include water temperature, hardness, as well as rCa/rMg ratio. The use of spring discharge data in conjunction with water chemistry data makes it possible to better understand water circulation in karstified carbonate aquifers. Cowell & Ford (1983), as well as Ede (1973), state that infrequent changes in spring water temperature indicate a diffuse-type spring, while frequent changes indicate a conduit-type spring (strong atmospheric precipitation effects). The rCa/rMg ratio is used to assess chemical water–rock interactions and water circulation times. The frequency of changes in geochemical and hydrological properties has often been used to determine water circulation patterns and to identify karst springs as conduit type and diffuse type. Frequent changes in ion concentrations suggest conduit-type springs, while less frequent changes suggest diffuse-type springs (Shuster & White 1971; Scanlon 1990). Musgrove & Banner (2004) found that there is a higher rCa/rMg ratio for diffuse recharge water due to longer contact between water and rocks. Water with a higher calcium concentration is used to classify springs as diffuse flow type, as opposed to conduit flow type (Desmarais & Rojstaczer 2002). The two largest springs in the Tatras are the Goryczkowe and Bystrej vaucluse springs, which could be used to provide drinking water to the nearby city of Zakopane. Both springs are found in Tatra National Park. Bystrej Górne Vaucluse Spring functions naturally. Some water is collected from Bystrej Dolne Vaucluse Spring and diverted to the nearby PTTK Hotel Górski Kalatówki. Some water is also obtained from Goryczkowe Vaucluse Spring and diverted to Myślenickie Turnie – a cable car transfer station run by the Polish Cable Car Company. Hence, the physical and chemical characteristics of water produced by the two springs vary naturally, which is why both are good candidates for a case study. The lack of human impact and a lack of studies in the potential contributing area of the selected springs make them attractive sites for research. The purpose of the research would be to determine the extent of the contributing area of Bystrej Górne Vaucluse Spring based on physical and chemical parameters as well as its overall functioning. In this paper, the two karst springs are analyzed concurrently. A synchronous study of two vaucluse springs makes it possible to show differences and similarities in terms of chemical parameters. The two springs are Goryczkowe Vaucluse Spring, where dye was used to determine its contributing area, and Bystrej Vaucluse Spring, where years of research have not produced results in the form of ponors in karst systems.

STUDY AREA

The Tatras are the highest mountain massif in the Carpathian mountain belt, with Mt Gerlach being the highest summit at 2,655 meters above sea level, and the highest alpine range between the Alps and the Caucasus mountains. The border between Poland and Slovakia runs virtually the entire length of the Tatras (Figure 1). The Tatra mountain region is protected as part of Tatra National Park, which is located both in Poland and Slovakia. The region is also legally protected in two other ways: (1) it is part of UNESCO's Biosphere Reserve and (2) it is part of the European Union's Natura 2000 ecological network. The Tatras are divided into three distinct geographic regions: (1) Bielskie Tatras, (2) High Tatras, and (3) Western Tatras. Each region has a different landscape, geology, plant life, and animal life.

Figure 1

Study area in the Polish Tatras and main karst flows (black rectangle – study area).

Figure 1

Study area in the Polish Tatras and main karst flows (black rectangle – study area).

As would be expected for any high mountain range, the Tatras possess several climate zones (Hess 1965), morphogenetic zones (Kotarba & Starkel 1972), vegetation zones (Piękoś-Mirkowa & Mirek 1996), soil zones (Skiba 2002), geoecological zones (Kotarba 1996) and climate changes in the vertical zones of the Polish Carpathians in the last 50 years (Bokwa et al. 2013). The mean annual precipitation total for the period 1966–2006 was 1,797.7 mm for Kasprowy Wierch Mountain (h = 1,991 m) and 1,117.6 mm for the nearby city of Zakopane (h = 857 m) (Żmudzka 2010). The largest amounts of precipitation are recorded during the summer, with the smallest in the winter. The number of days with snow cover ranges from about 100 per year at the foot of the Tatra mountain range to 220 per year on Kasprowy Wierch Mountain (Falarz 2000–2001). The mean annual air temperature ranges from −0.8 °C on Kasprowy Wierch Mountain to 3.3 °C on the Myślenickie Turnie Ridge and 4.9 °C in the nearby city of Zakopane (Niedźwiedź 1992). There are five vegetation belts in the Tatra Mountains – lower belt, upper belt, dwarf pine belt, mountain meadow belt, and rocky mountain belt (Mirek & Piękoś-Mirkowa 1992). The lower and upper vegetation belts are covered with spruce trees of varying age. The lower vegetation belt is currently being diversified by planting beech and fir (Kozłowska 2009). The studied springs are located in the Polish part of the Western Tatras (Figure 1), which are formed primarily of metamorphic rocks in the south and carbonate rocks in the north. The region's crystalline core is covered by summit series and slope series formed of sedimentary rocks such as limestone and dolomite (Bac-Moszaszwili et al. 1979; Głazek 1995). This type of geology creates favorable conditions for water infiltration and groundwater circulation. The Goryczkowe and Bystrej Górne vaucluse springs are both located in the Western Tatras in Bystrej Valley (Figures 25). Both springs are found at similar elevations: 1,175.8 m, approximately 1,165 m, respectively (Małecka 1993, 1997; Barczyk 2008). Goryczkowe Vaucluse Spring is found in Goryczkowy Potok Valley at the base of Myślenicka Turnia Mountain. Bystrej Górne Vaucluse Spring is found on the side of Kalacka Turnia Mountain. The primary karst system of the Goryczkowe Vaucluse Spring developed in Middle Triassic limestone found in a summit series, while that of the Bystrej Vaucluse Spring developed in Middle Triassic carbonate rock as well as Malm and Neocomian found in summit series (Małecka 1997; Barczyk 2008). Oleksynowa & Komornicki (1996) asserted that both springs are crystalline type (moraine type). According to Łajczak (1996), the contributing area of Goryczkowe Vaucluse Spring includes a crystalline part and a sedimentary part, while Bystrej Vaucluse Spring is recharged by waters exiting Giewont Massif. According to Barczyk (2008), the contributing area of Goryczkowe Vaucluse Spring includes the karstified Myślenickie Turnie massif, alluvial and moraine valley deposits, and karst systems in the Sucha Woda catchment. On the other hand, the primary contributing area of Bystrej Górne Vaucluse Spring has not been extensively studied. Małecka et al. (2002a, b) suggest that deep groundwater circulation under the Bystra stream channel may be drawing water from numerous karst channels and caves and groundwater aquifers. Currently, it is assumed that the primary contributing area for both Bystrej Górne Vaucluse Spring and Bystrej Dolne Vaucluse Spring is the Giewont Massif, and both springs constitute a drainage system for Bystra Cave (Małecka 1993, 1997).

Figure 2

Bystrej Górne Vaucluse Spring – low discharge.

Figure 2

Bystrej Górne Vaucluse Spring – low discharge.

Figure 3

Bystrej Górne Vaucluse Spring – high discharge.

Figure 3

Bystrej Górne Vaucluse Spring – high discharge.

Figure 4

Goryczkowe Vaucluse Spring – low discharge.

Figure 4

Goryczkowe Vaucluse Spring – low discharge.

Figure 5

Goryczkowe Vaucluse Spring – high discharge.

Figure 5

Goryczkowe Vaucluse Spring – high discharge.

DATA AND METHODS

The research was conducted over the course of 1 year from November 2011 to October 2012. One half liter water sample was collected once a month from each spring for a total of 24 samples for the purpose of synchronous analysis. Water temperature, electrical conductivity [EC25°C], and pH were measured in the field using a multifunctional WTW 350i meter with an integrated POLYPLAST PRO glass electrode manufactured by Hamilton as well as an LR-325/01 conductometric sensor made by WTW (constant k = 0.1) with a built-in PT-1000 temperature sensor. Water levels and spring discharge were measured using a water current meter with an OTT ADC acoustic discharge sensor.

Chemical analysis of all water samples was performed using ion chromatography at the Hydrochemical Laboratory of the Institute of Geography and Spatial Management at Jagiellonian University. Water samples were first filtered using a 0.45 µm syringe filter. Next, the content of each sample was determined using a DIONEX ICS-2000 ion chromatograph. Water samples were analyzed for the following 14 ions: Ca2+, Mg2+, Na+, K+, , SO42–, Cl, Li+, F, Br, NH4+, NO2, NO3, and PO43–. The last four ions are known as biogenic ions. The accuracy of the analytical method was estimated using a relative standard deviation for 12 consecutive analyses of a standard solution. The error for the anion solution averaged about 1% for each ion analyzed. The error for the cation solution averaged 0.4% for each ion analyzed. Close to 100% of the desired product was recovered, which proved to be an excellent outcome and confirmed the efficacy of the method used. The product recovery rate varied 1% from ion to ion. The quality of the chromatograph used was continuously tested using certified reference materials. The reference materials used to test the chromatograph included rainwater with a low pH (A Es-02 [Lot No. 901]) and river water (Trois-94 [Lot No. 306]). The accuracy of the cation determination in the case of metals was additionally confirmed by comparing with inductively coupled plasma mass spectrometry (ICP–MS) output. Tables on detection limits, mean ion recovery values, error analysis based on the ion balance, and parameters of the chromatographic system used are available in the monograph Temporal and spatial variation in the physical and chemical characteristics of water in Tatra National Park (Żelazny 2012). It is important to note that water in the Tatra Mountains has a very low ion content: 56.1% of the 1,018 Tatra Mountain springs analyzed are characterized by an ion content of less than <3 mval L−1. The mean relative error based on the ion balance was calculated to be 2.28% and the median was 2.14% (Żelazny 2012).

Mineral content (TDS) was calculated as the total of all the ions identified. Total hardness was calculated as the total of rCa2+ and rMg2+ expressed in mval L−1. A water saturation index was calculated for calcite (SIc) and dolomite (SId) (Parkhurst & Appelo 2013). Saturation calculations were performed using PHREEQC Interactive 3.0 software.

It was assumed that positive values of the saturation index represent the precipitation of calcite or dolomite, while negative values represent dissolution. A state of equilibrium was designated using a value of zero with a fluctuation of ±5% log of the equilibrium constant. Principal component analysis (PCA) was used to identify factors affecting the physical and chemical characteristics of the tested water samples. The Kaiser criterion was used to select the most important factors. Analysis of variance (ANOVA) and Scheffe's post hoc test (p = 0.95) were used to check for statistically significant differences between average values of selected physical and chemical characteristics of spring water for different seasons. In this paper, it is assumed that each season consists of 3 months: (1) winter – December, January, February; (2) spring – March, April, May; (3) summer – June, July, August; (4) autumn – September, October, November. Scheffe's test was used to test for significant differences between the studied springs in terms of chemistry and physical characteristics. A lack of differences would suggest that the contributing areas of each spring feature a similar geological structure. In this paper, several basic statistics are used to analyze data including the median (Me), mean, minimum (min), maximum (max), as well as quantiles (quartiles: Q25% and Q75%; deciles: D10% and D90%). The coefficient of variation (Cv), defined as the ratio of the standard deviation and the mean, is used to describe the variation of parameters and is expressed as a percentage.

RESULTS AND DISCUSSION

The mean discharge of Goryczkowe Vaucluse Spring during the study period was approximately 500 L s−1, which was almost double the rate for Bystrej Górne Vaucluse Spring (Table 1). Based on the Meinzer (1927) classification, Goryczkowe Vaucluse Spring qualifies as a Class 2 spring, while Bystrej Górne Vaucluse Spring qualifies as a Class 3 spring. However, at high water stages, Bystrej Górne Vaucluse Spring may be classified as a Class 2 spring. Fifteen parameters of water were analyzed. In most cases, differences between mean values were not significant (Figure 6). The water temperature for Goryczkowe Vaucluse Spring was higher by an average of 0.4 °C. However, the mean water temperature of both springs oscillated at about 4.5 °C, and exhibited only small fluctuations during the study period. This water temperature range corresponds to the mean annual air temperature in the region, which is 4 to 6° C (Hess 1965). A higher pH was noted for Goryczkowe Vaucluse Spring versus Bystrej Górne Vaucluse Spring. The mean annual pH for both springs oscillates at about 8, and Cv oscillates at about 2%. The same pattern held true for mineral content (TDS): Bystrej Górne Vaucluse Spring (103.6 mg L−1), Goryczkowe Vaucluse Spring (84.1 mg L−1). Hence, these are very low mineral content waters, which is linked with the drainage of contributing areas with similar geology resistant to leaching. The lack of significant differences in the physical and chemical parameters of water obtained from the two studied springs leads to the conclusion that both springs' contributing areas may be similar in terms of geology. The largest anion concentration in the water samples obtained from Goryczkowe and Bystrej Górne Springs is that of , while the largest cation concentration is that of Ca2+ (Table 1). The concentrations of other ions were found to be much smaller. The biogenic ion with the largest concentration was usually . The concentrations of , , Li+, Br, and F were usually below detection limits. The cation order based on concentration was the following for both springs: Ca2+ > Mg2+ > Na+ > K+. The anion order based on concentration was the following for both springs: . The sequence of ion concentrations shows that these water samples represent typical shallow circulation groundwater in the temperate climate zone. The analysis of relationships between ion concentrations, as shown in the Piper diagram (Figure 7) and that shown in Table 2 indicate that the water chemistry of the studied springs varies. Lodowe Źródło Vaucluse Spring is the most typical Tatra vaucluse spring and drains exclusively calcium and dolomite formations. Its mineral content is the highest in this study. Chochołowskie and Goryczkowe vaucluse springs are characterized by low values of chemical parameters, as they drain the crystalline core of the Tatras and their period of contact with karst rocks is brief. The anion with the smallest Cv in the case of both springs was . The cation with the smallest Cv in the case of both springs was Na+. The largest Cv values for Goryczkowe Vaucluse Spring were those of K+ and . The largest Cv values for Bystrej Górne Vaucluse Spring were those of and Cl. The Cv of the concentration of Ca2+ and ions indicates a high degree of variance in the two studied springs; however, research on other springs in the Tatra region has shown that the concentration of Ca2+ and ions is very stable over the course of the year (Cv <15%) (Wolanin & Żelazny 2010; Żelazny et al. 2013a, b). Karst springs characterized by Ca2+ variances of more than 5% experience rapid recharge and transmission (Vesper & White 2004). Conduit springs are characterized by larger variances (Cv =10–24%) in water hardness over the course of the year than diffuse springs (Cv < 5%) (Shuster & White 1971). Water hardness of Goryczkowe Vaucluse Spring water averaged 1.08 mval L−1 and its coefficient of variation was 25.5%, while the corresponding values for Bystrej Górne Vaucluse Spring were 1.31 mval L−1 and 20.0% (Table 1). The calcium (rCa) to magnesium (rMg) ratio in Goryczkowe Vaucluse Spring water was determined to be 3.11 (mean value), while that of Bystrej Górne Vaucluse Spring water was −2.90. The calculated rCa/rMg ratios suggest that the studied springs' waters circulate within dolomite limestone or karst systems formed of limestone and dolomite (White 2006). However, the slightly higher average rCa/rMg ratio for Goryczkowe Vaucluse Spring may indicate that its waters flow primarily through limestone (Jacobson & Langmuir 1970). However, this type of interpretation is insufficient. As mentioned earlier, the TDS of both studied springs is low, which indicates that the tested water's composition is shaped in geological formations resistant to leaching. These formations may include solely rocks of the crystalline core of the Tatras (e.g., granitoid, gneiss, schist). Goryczkowe Vaucluse Spring is recharged by waters drained from High Tatra granitoids. The higher mineral content of waters exiting Bystrej Górne Vaucluse Spring suggests that these waters originate on slopes composed of more soluble rocks. Figure 8 shows the mean value of EC25°C and the concentration of Mg2+ versus 1,018 springs in Tatra National Park. When compared with empirical density functions calculated with reference to lithological conditions, water obtained from Goryczkowe and Bystrej Górne vaucluse springs appears to resemble water obtained from springs draining the Tatra crystalline core (Nos 1, 2 and 4) rather than springs draining sedimentary rocks such as dolomite and limestone (No. 5). On the other hand, the concentration of the magnesium ion is markedly higher in springs draining Goryczkowe-type granite. Hence, the lower rCa/rMg ratio for Bystrej Górne Vaucluse Spring water most likely results from drainage of the western, upper part of the Tatra crystalline core formed of Goryczkowe-type granite as well as some gneiss and schist (Figure 9). Values of the calcite saturation index (SIc) ranged from −0.25 to −1.01 for Goryczkowe Vaucluse Spring, and from −0.09 to −1.09 for Bystrej Górne Vaucluse Spring (Table 1). Next, the SId ranged from −1.14 to −2.81 for Goryczkowe Spring, and from −0.85 to −2.88 for Bystrej Górne Vaucluse Spring. Negative values of SIc and SId indicate that both studied springs are unsaturated with respect to calcite and dolomite and aggressiveness with respect to calcium carbonate and dolomite. The conduit system where water flows rapidly and reacts quickly to rainstorms is characterized by low saturation index values (Jawad & Hussien 1986). Figure 10 shows seasonal changes in the physical and chemical characteristics of water obtained from Goryczkowe and Bystrej Górne vaucluse springs. The highest values were noted for the winter months (January–March) and the lowest for spring and summer (April–July). The opposite is true of discharge in the case of both springs. High discharge was noted for spring and summer, and low discharge for winter. High discharge values are associated with the melting of snow cover during the spring and high precipitation in the summer. Spring water temperature patterns are also a key indicator of seasonal change (Shuster & White 1971). High water temperatures were noted for Goryczkowe Vaucluse Spring in the summer and low temperatures were noted in the winter, according to research by Davies (1991) and Wicks (1997). The opposite pattern was observed in the case of Bystrej Górne Vaucluse Spring – low water temperatures in the summer and high temperatures in the winter. This suggests that the spring's water is supplied via a different circulation system. Two factors that differentiate the contributing areas of the studied springs in terms of water temperature are water circulation patterns and the presence of lakes above ponors in Sucha Woda Valley, where water that exits Lake Zielony Staw and other sources is absorbed by the karst system of Goryczkowe Vaucluse Spring via ponors. There are no lakes in Bystrej Valley; therefore, water enters Giewont Massif, formed of karst rocks and caves, via diffuse flow. ANOVA results indicate that seasonal differences between mean values of discharge as well as physical and chemical characteristics of the studied springs are not statistically significant. A lack of differences in mean values may suggest that chemical behavior affects the properties of each vaucluse spring (Raeisi & Karami 1997).

Table 1

Physical and chemical characteristics of two vaucluse springs

 Discharge Temperature   EC25°C Hardness TDS                         
 (L s−1(°C) pH (μS cm−1(mval·L−1(mg L−1Ca2+ Mg2+ Na+ K+ NH4+ HCO3 SO42− Cl NO3 rCa/rMg SIc SId 
Mean Bystrej Górne Vaucluse Spring 258 4.4 7.91 123.8 1.31 103.6 19.43 4.08 0.91 0.33 0.023 70.93 5.52 0.44 1.80 2.90 − 0.55 − 1.78 
Median 244 4.4 7.93 123.8 1.31 101.1 19.35 4.29 0.92 0.33 0.023 69.43 5.64 0.40 1.75 2.87 − 0.52 − 1.70 
Min 197 4.3 7.46 92.0 0.92 79.3 13.76 2.76 0.76 0.25 0.002 55.10 4.27 0.31 1.61 2.61 − 1.09 − 2.88 
Max 339 4.6 8.25 155.2 1.69 133.1 25.38 5.15 1.14 0.44 0.061 91.51 6.71 0.82 2.12 3.50 − 0.09 − 0.85 
Q25% 217 4.4 7.69 112.0 1.14 91.6 16.75 3.43 0.83 0.27 0.003 62.73 4.57 0.31 1.66 2.75 − 0.80 − 2.27 
Q75% 300 4.5 8.18 138.5 1.48 115.8 22.32 4.65 0.94 0.38 0.040 78.63 6.27 0.51 1.98 2.98 − 0.29 − 1.21 
Cv (%) 19.6 2.2 3.3 16.8 20.0 16.6 20.4 20.1 10.5 19.4 89.2 16.0 16.4 35.1 9.8 8.1 57.1 36.5 
Mean Goryczkowe Vaucluse Spring 484 4.8 8.13 105.2 1.08 84.1 16.28 3.28 0.95 0.43 0.021 51.24 9.67 0.40 1.73 3.11 − 0.55 − 1.79 
Median 404 4.8 8.14 103.4 1.01 80.8 15.07 3.19 0.95 0.31 0.010 49.77 9.36 0.36 1.73 2.93 − 0.52 − 1.70 
Min 105 4.6 7.87 61.2 0.60 48.2 9.55 1.52 0.74 0.23 0.002 29.40 4.36 0.29 1.61 2.71 − 1.01 − 2.81 
Max 1164 5.0 8.40 145.0 1.55 117.7 23.49 4.64 1.15 1.95 0.066 72.80 15.34 0.69 1.90 4.27 − 0.25 − 1.14 
Q25% 194 4.8 8.01 91.1 0.88 73.3 13.68 2.61 0.90 0.24 0.003 46.26 6.54 0.32 1.63 2.83 − 0.66 − 2.02 
Q75% 656 4.9 8.26 121.4 1.33 99.7 19.57 4.24 0.99 0.35 0.043 59.56 13.13 0.46 1.82 3.17 − 0.38 − 1.41 
Cv (%) 76.9 2.4 2.0 22.5 25.5 23.2 24.0 30.7 11.1 111.7 105.4 22.9 39.0 28.7 5.9 15.0 44.1 30.4 
 Discharge Temperature   EC25°C Hardness TDS                         
 (L s−1(°C) pH (μS cm−1(mval·L−1(mg L−1Ca2+ Mg2+ Na+ K+ NH4+ HCO3 SO42− Cl NO3 rCa/rMg SIc SId 
Mean Bystrej Górne Vaucluse Spring 258 4.4 7.91 123.8 1.31 103.6 19.43 4.08 0.91 0.33 0.023 70.93 5.52 0.44 1.80 2.90 − 0.55 − 1.78 
Median 244 4.4 7.93 123.8 1.31 101.1 19.35 4.29 0.92 0.33 0.023 69.43 5.64 0.40 1.75 2.87 − 0.52 − 1.70 
Min 197 4.3 7.46 92.0 0.92 79.3 13.76 2.76 0.76 0.25 0.002 55.10 4.27 0.31 1.61 2.61 − 1.09 − 2.88 
Max 339 4.6 8.25 155.2 1.69 133.1 25.38 5.15 1.14 0.44 0.061 91.51 6.71 0.82 2.12 3.50 − 0.09 − 0.85 
Q25% 217 4.4 7.69 112.0 1.14 91.6 16.75 3.43 0.83 0.27 0.003 62.73 4.57 0.31 1.66 2.75 − 0.80 − 2.27 
Q75% 300 4.5 8.18 138.5 1.48 115.8 22.32 4.65 0.94 0.38 0.040 78.63 6.27 0.51 1.98 2.98 − 0.29 − 1.21 
Cv (%) 19.6 2.2 3.3 16.8 20.0 16.6 20.4 20.1 10.5 19.4 89.2 16.0 16.4 35.1 9.8 8.1 57.1 36.5 
Mean Goryczkowe Vaucluse Spring 484 4.8 8.13 105.2 1.08 84.1 16.28 3.28 0.95 0.43 0.021 51.24 9.67 0.40 1.73 3.11 − 0.55 − 1.79 
Median 404 4.8 8.14 103.4 1.01 80.8 15.07 3.19 0.95 0.31 0.010 49.77 9.36 0.36 1.73 2.93 − 0.52 − 1.70 
Min 105 4.6 7.87 61.2 0.60 48.2 9.55 1.52 0.74 0.23 0.002 29.40 4.36 0.29 1.61 2.71 − 1.01 − 2.81 
Max 1164 5.0 8.40 145.0 1.55 117.7 23.49 4.64 1.15 1.95 0.066 72.80 15.34 0.69 1.90 4.27 − 0.25 − 1.14 
Q25% 194 4.8 8.01 91.1 0.88 73.3 13.68 2.61 0.90 0.24 0.003 46.26 6.54 0.32 1.63 2.83 − 0.66 − 2.02 
Q75% 656 4.9 8.26 121.4 1.33 99.7 19.57 4.24 0.99 0.35 0.043 59.56 13.13 0.46 1.82 3.17 − 0.38 − 1.41 
Cv (%) 76.9 2.4 2.0 22.5 25.5 23.2 24.0 30.7 11.1 111.7 105.4 22.9 39.0 28.7 5.9 15.0 44.1 30.4 
Table 2

Mean physical and chemical characteristics of three vaucluse springs in Tatra National Park (Żelazny et al. 2013a)

Feature Units Chochołowskie Vaucluse Spring Źródło Lodowe Vaucluse Spring Olczyskie Vaucluse Spring 
Temperature (°C) 5.0 4.5 4.5 
pH (pH) 8.01 8.08 8.24 
EC25°C (μS cm−1178.3 201.6 131.4 
TDS (mg L−1145.9 176.9 111.9 
Ca2+ 24.74 36.21 16.83 
Mg2+ 8.33 5.62 6.95 
Na+ 0.78 0.44 0.78 
K+ 0.43 0.51 0.34 
 94.11 126.15 77.49 
 15.01 5.62 7.03 
Cl 0.51 0.49 0.42 
 1.98 1.78 2.03 
Feature Units Chochołowskie Vaucluse Spring Źródło Lodowe Vaucluse Spring Olczyskie Vaucluse Spring 
Temperature (°C) 5.0 4.5 4.5 
pH (pH) 8.01 8.08 8.24 
EC25°C (μS cm−1178.3 201.6 131.4 
TDS (mg L−1145.9 176.9 111.9 
Ca2+ 24.74 36.21 16.83 
Mg2+ 8.33 5.62 6.95 
Na+ 0.78 0.44 0.78 
K+ 0.43 0.51 0.34 
 94.11 126.15 77.49 
 15.01 5.62 7.03 
Cl 0.51 0.49 0.42 
 1.98 1.78 2.03 
Figure 6

Physical and chemical characteristics of Goryczkowe and Bystrej Górne spring water. A lack of significant differences between the two springs is marked with a rectangle.

Figure 6

Physical and chemical characteristics of Goryczkowe and Bystrej Górne spring water. A lack of significant differences between the two springs is marked with a rectangle.

Figure 7

Water chemistry of Vaucluse springs in the Tatras expressed using a Piper diagram.

Figure 7

Water chemistry of Vaucluse springs in the Tatras expressed using a Piper diagram.

Figure 8

Electrolytic conductivity and concentration of magnesium in Tatra area vaucluse springs versus all 1,018 springs in the Tatra Mountains, expressed using empirical probability density functions for chemical characteristics of spring water in relation to geological and lithological condition.

Figure 8

Electrolytic conductivity and concentration of magnesium in Tatra area vaucluse springs versus all 1,018 springs in the Tatra Mountains, expressed using empirical probability density functions for chemical characteristics of spring water in relation to geological and lithological condition.

Figure 9

Most probable contributing area for Bystrej Górne Vaucluse Spring.

Figure 9

Most probable contributing area for Bystrej Górne Vaucluse Spring.

Figure 10

Seasonal changes in the physical and chemical characteristics of Goryczkowe Vaucluse Spring and Bystrej Górne Vaucluse Spring.

Figure 10

Seasonal changes in the physical and chemical characteristics of Goryczkowe Vaucluse Spring and Bystrej Górne Vaucluse Spring.

PCA was used to identify two main factors (Table 3) based on discharge, water temperature, conductivity, mineral content, pH, and selected ion concentrations. The two factors explain 78.28% of variation in the case of Goryczkowe Vaucluse Spring and 85.47% of variation in the case of Bystrej Górne Vaucluse Spring. In the case of Factor 1, the greater the spring discharge, the lower the values of physical and chemical characteristics and ion concentrations in Goryczkowe and Bystrej Górne vaucluse springs. This relationship is typical of groundwater dilution processes driven by low mineral content snowmelt and precipitation water (Evans et al. 1996; Bhangu & Whitfield 1997; Piatek et al. 2009). It was observed for Goryczkowe Spring that water temperature increases with increasing discharge. The opposite tendency was noted for Bystrej Górne Vaucluse Spring. The negative relationship between spring discharge and the concentration of Ca2+, Mg2+, Na+, and as well as the correlation between the four ions indicate that these ions come from rock weathering (Caissie et al. 1996). Next, in the case of Factor 2 for Bystrej Górne Vaucluse Spring, the higher the water temperature, the higher the pH and the lower the concentrations of K+, Na+, Cl, and . In the case of Goryczkowe Vaucluse Spring, the higher the water temperature, the higher the pH and concentration of and the lower the concentration of , Cl, and NO3 (Factor 2). This factor is associated with the absorption of ions needed to sustain life in the catchment. The concentration of biogenic ions usually decreases during the vegetation season due to ion absorption by plants (Semkin et al. 1994; Campbell et al. 2000; Sullivan & Drever 2001; Butturini & Sabater 2002; Clark et al. 2004; Lovett et al. 2005; Toran & White 2005).

Table 3

Factor loadings of physical and chemical characteristics of Goryczkowe Vaucluse Spring and Bystrej Górne Vaucluse Spring

Vaucluse spring Goryczkowe
 
Bystrej Górne
 
Feature Factor 1 Factor 2 Factor 1 Factor 2 
Discharge 0.94  0.86  
Temperature 0.48 − 0.52 − 0.47 − 0.49 
pH  − 0.49 − 0.65 − 0.63 
EC25°C 0.94  0.98  
TDS 0.94  0.98  
Ca2+ 0.98  0.98  
Mg2+ 0.92  0.94  
Na+ 0.75   0.88 
K+ − 0.61  − 0.59 0.68 
NH4+ − 0.63 0.67 0.78  
 0.89  0.96  
SO42– 0.72 − 0.55 0.90  
Cl − 0.57 0.76 0.85 0.45 
NO3 − 0.55 0.79 0.83 0.47 
Variance (%) 56.98 21.30 66.46 19.01 
Vaucluse spring Goryczkowe
 
Bystrej Górne
 
Feature Factor 1 Factor 2 Factor 1 Factor 2 
Discharge 0.94  0.86  
Temperature 0.48 − 0.52 − 0.47 − 0.49 
pH  − 0.49 − 0.65 − 0.63 
EC25°C 0.94  0.98  
TDS 0.94  0.98  
Ca2+ 0.98  0.98  
Mg2+ 0.92  0.94  
Na+ 0.75   0.88 
K+ − 0.61  − 0.59 0.68 
NH4+ − 0.63 0.67 0.78  
 0.89  0.96  
SO42– 0.72 − 0.55 0.90  
Cl − 0.57 0.76 0.85 0.45 
NO3 − 0.55 0.79 0.83 0.47 
Variance (%) 56.98 21.30 66.46 19.01 

Loadings ≥0.70 are bold, loadings less than 0.40 are excluded.

The weaker relationship between water temperature and the concentration of in Bystrej Górne Spring indicates that catchment biological activity is less important in this particular case. Factors that differentiate the springs' contribution areas include the presence of extensive woodland areas on slopes in the potential contribution area of Bystrej Górne Vaucluse Spring and the presence of lakes in the contribution area of Goryczkowe Vaucluse Spring. Additional research is needed on seasonal changes in nitrate concentration in spring water.

CONCLUSIONS

Based on physical and chemical characteristics, water obtained from the two studied vaucluse springs is typical of low mineral content waters found in temperate climate zones, with hydrogen carbonate as the main anion and calcium as the main cation.

Changes in the physical and chemical characteristics of water in both springs follow a similar pattern over the course of the year, with several exceptions. Seasonal changes in the physical and chemical characteristics of water in both springs occur due to the dilution of groundwater with low mineral content precipitation water, which is a key driver of change. The second primary driver of change is catchment biological activity, as manifest by a decrease in the concentration of biogenic ions during the vegetation season.

The two springs are both similar and different in a number of ways. The physical and chemical characteristics of water in both springs are similar in terms of ion concentrations, hydrochemical indicators, and seasonal changes therein, which suggests that their source aquifers are similar, but not the same. An analysis of spring water chemistry based on empirical density functions makes it possible to show that the most likely contributing area of Bystrej Górne Vaucluse Spring is the western crystalline part of Bystrej Valley.

ACKNOWLEDGEMENTS

The research is a part of the following project: ‘Factor determining spatial variability and dynamics of water chemical composition in Tatra National Park’, financed by the Polish Ministry of Science and Higher Education (MNiSzW–N305-081 32/2824).

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