The water quality status of the Turawa Reservoir was assessed, taking previous studies and the current status into account. Biological elements and the chemical and sanitary status of the reservoir waters and feeder waters were considered. Pollution sources were also identified.
4.1. Water quality in the Turawa Reservoir and feed waters
Studies of the reservoir water quality by Polish scientific research centres date back several decades. The reservoir has also aroused the interest of foreign scientists 28,29. Their main goal was to assess the biological and chemical threat to the ecosystem and search for methods to revitalise the reservoir 30,31. Water quality studies of the Mała Panew River and the waters of the Turawa Reservoir are also carried out regularly by the Regional Department of Environmental Monitoring in Opole. For the waters of the Mała Panew River, control points have been set at locations described by geographic coordinates: 50.621246 N, 18.463813 E (Zawadzkie, site no. 12, Fig. 2a) and 50.70047 N, 18.18794 E (Jedlice, site no. 18, Fig. 2a). For the waters of the Turawa Reservoir, the measuring point was determined at the place described by the coordinates: 50.73584 N, 18.09328 E (site no. 37, Fig. 2b) 22.
In terms of biological elements, the condition of Turawa Reservoir waters was classified as poor (2010–2012 and 2018–2019) and moderate (2013–2016) 22. The results of our research, conducted in 2019–2021 (Table 1), indicate that, in terms of biological elements, the condition of the reservoir waters varied from moderate to poor, depending on the indicator, with the majority of measurements indicating poor condition in terms of IFPL and IO indicators. Our research covered the waters of the littoral zone of the northern shore of the reservoir (Fig. 2b, sites 32–36). It can be concluded that the condition of the waters, in terms of biological elements, has deteriorated over two decades, with our research covering the littoral zone, while the research conducted by the Regional Department of Environmental Monitoring in Opole covered the bottom, at the outflow of the Mała Panew River from the reservoir (site 37, Fig. 2b).
Tests conducted in 2019–2021 on oxygen indicators BOD5 and CODCr in Turawa Reservoir waters (Table 2) indicate that the average values remain in Class I (CODCr ≤ 25 mgO2 L− 1) and Class II (BOD5 > 3.0–6.0 mgO2 L− 1) relative to the limit values set for river water bodies of surface water type 0, namely dam reservoirs 15, with exceedances of the limit value registered for BOD5. Much higher CODCr values were registered in waters of the Mała Panew River (average 71.9 mgO2 L− 1) and the Libawa River (average 59.7 mgO2 L− 1). In comparison, in the waters of the Mała Panew River (Jedlice, site No. 18, Fig. 2a) in 2005–2018, average values of BOD5 in the range of 1.5–3.3 mgO2 L− 1and CODMn = 6.5–24 mgO2 L− 1were recorded 22. Other studies conducted in 2002–2005 indicated average values of BOD5 = 2.16 mgO2 L− 1and CODCr = 21.4 mgO2 L− 1at the inflow to the reservoir and BOD5 = 3.58 mgO2 L− 1and CODCr = 34.1 mgO2 L− 1 in the waters of Turawa Reservoir 32. In studies conducted in 2010–2015, the average value of BOD5 was set at 2.2 mgO2 L− 1 33. Analysing data from the last two decades, it can be concluded that BOD5 rates are comparable.
Disturbingly high CODCr values were recorded in the waters of the Mała Panew River during the implementation of our research, influenced by measurements made at sites 2–4 and 8–11 (Fig. 4a), and relatively high values of both indicators were recorded in June 2020 (Fig. 5a). In the waters of the reservoir, relatively high values of BOD5 and CODCr were recorded in September 2020, which could be caused by increased oxygen demand due to the decomposition of organic matter (algae and cyanobacteria). Positive correlations of the increase in BOD5 and CODCr values with increasing organic matter are indicated by other authors 34. In terms of total organic carbon (TOC), the waters of the Turawa Reservoir were classified in Class II: >10–15 mgC L− 1 15: the average in 2009, 2011 and 2014 was set at 11.4 mgC L− 1 35. In 2016 the yearly mean was 11.2 mgC L− 1 22.
Studies of nutrient parameters carried out in 2019–2021 (Table 2) indicate that Class II was exceeded concerning the limits of NO3-N and TP set for river water bodies of surface water type 0, namely dam reservoirs (limits for Class II: NO3-N ≤ 5.0 mg L− 1, TP ≤ 0.4 mg L− 1) and that Class II was maintained concerning TN: 5 < TN ≤ 10 mg L− 1 15. Higher average NH4-N concentrations were recorded in the reservoir recharge waters compared with the reservoir waters, with the results of measurements at sites 11–13 having a decisive influence on the average value (Fig. 4b). There was also an increase in other nutrient indicators at sites 11–13 (Fig. 4b). Differences in the mean values of NO3-N from Tables 2 and 3) reach 30% and are due to different sampling locations and periods. In the reservoir waters, the highest values of biogenic indicators were recorded in the southern part of the reservoir (Fig. 4f) at sites 32–36 (Fig. 2b).
Seasonal changes in TN and TP in the waters of the Mała Panew River (Fig. 5b) and reservoir waters (Fig. 5d) are difficult to interpret. A detailed analysis of the data for 2019–2021 indicates that the high variability of TN and NO3-N concentrations in the waters of the Mała Panew River is influenced by surface runoff from agricultural land 26. Agricultural land, as a source of nitrogen compounds in surface waters, is also indicated by other authors 36,37. In the reservoir waters the concentrations of biogenic ions show a decreasing trend during the growing season (Fig. 6d), contrary to the values of TN, for which the highest values of concentrations were registered in June and August (Fig. 5d). This may be influenced by the increase in the concentration of ammonium and organic nitrogen (Kjeldahl nitrogen – TKN) and the intensity of the nitrification and denitrification processes 38. The average values of nutrient indicator concentrations in the reservoir waters, determined in 2002–2005, were: NO3-N 2.99 mg L− 1, NO2-N 0.13 mg L− 1, NH4-N 0.33 mg L− 1 and PO4-P 0.20 mg L− 1. At the Mała Panew River tributary to the reservoir, they were: NO3-N 10.11 mg L− 1, NO2-N 0.14 mg L− 1, NH4-N 0.45 mg L− 1 and PO4-P 0.30 mg L− 1 32. The average values of TN and TP indicators from 2010–2015 in the waters of the Mała Panew River were, respectively: 3.9 mg L− 1 and 0.135 mg L− 1 33 and were comparable to the average values determined in 2019–2021 (Table 2).
According to 22 the water chemical condition of the Turawa Reservoir and the Mała Panew River in 2013–2015 was assessed as being below the “good” status, unlike the waters of the Libawa River, whose condition, with the exception of NH4-N content, was determined as Class I. A significant improvement in the quality of the waters of the Mała Panew River in terms of NO3-N and PO4-P contents can be found compared with the results of the 2002–2005 study. The ionic composition of Turawa Reservoir waters shows significant differences in the distribution of concentrations of biogenic ions: NO2−, NO3−, PO43− and NH4+ (Fig. 6c), depending on the sampling location. The relative concentrations of biogenic ions, which were higher than the average value, were recorded mainly in the north-eastern part of the reservoir and at the tributary of the Mała Panew River. The distribution of concentrations of the other analysed ions: F−, Cl−, Br−, SO42−, Na+, K+, Ca2+ and Mg2+ are within the range: s ≤ mean, indicating a relatively uniform distribution of these ions in the reservoir waters. In 2013, a study of the ionic composition of 24 water reservoirs in the Opole Province (PL) was conducted, including the Turawa Reservoir 24. In comparison with other dam reservoirs located in Opole Province (Otmuchów Reservoir and Nysa Reservoir), Turawa Reservoir had higher concentrations of most of the ions studied: F−, Cl−, Br−, NO3−, SO42−, Na+, K+ and Ca2+, as well as higher values of water conductivity and pH.
The conductivity of Turawa Reservoir water (Table 4) was within Class I of the water quality of surface water type 0, namely dammed reservoirs (κ ≤ 1000 µS cm− 1 15). In the feed waters, the average conductivity values were comparable, and the maximum values did not exceed 1000 µS cm− 1.
The issue of concern has become the alkaline reaction of the reservoir waters (Table 4). The average pH value exceeds the value designated for water quality class I of surface water type 0, namely dammed reservoirs 15. The alkalinity of the reservoir waters is also indicated by previous studies. In the years 2002-05 the pH in the range 7.60–9.95 was determined 32. In 2013 pH higher than 10 was observed 24. The studies carried out in 2011-14 indicate the pH values in the range 7.70–9.90 20.
Alkaline water pH values, as a factor promoting cyanobacterial blooms, have been pointed out by other authors 39–41. However, it should be noted that a large increase in pH values in the reservoir waters was observed during the summer, the season of intense algal blooms (Fig. 7) and, in the reservoir feed waters, determined pH values were contained within the limits 5.70–8.12 (Table 4). Therefore, it can be concluded that the increase in pH during summer is not influenced by the quality of the feed water, but is caused by biochemical processes occurring in the reservoir waters.
Concentrations of heavy metals Cr, Zn, Cu, determined in the waters of the Turawa Reservoir and in the feed waters (Table 5), do not exceed the limits set for surface waters: Cr ≤ 50 µg L− 1, Zn ≤ 1000 µg L− 1, Cu ≤ 50 µg L− 1 15. The average values of Ni and Pb in the Mała Panew and the Libawa River waters exceed the values of average annual concentrations of chemical status indicators for surface water bodies (Ni ≤ 4 µg L− 1, Pb ≤ 1.2 µg L− 1) while maintaining the quality standards for maximum allowable concentrations (Ni ≤ 34 µg L− 1, Pb ≤ 14 µg L− 1). Cd concentrations were below the analytical method’s limit of quantification. However, analysis of 22 data from the last two decades indicates significant Cd concentrations in 2011 and 2014 in the waters of the Mała Panew River, above and below the Turawa Reservoir, based on which the chemical status of the waters was classified as being below the “good” status. In 2015, in the waters of the Mała Panew River above the reservoir, Cd concentrations also contributed to poor water assessment (below the “good” status). In 2018, the waters of the Mała Panew River were classified as Class I for concentrations of Cr, Ni, Zn, Cu, Cd and Pb. Cadmium concentrations in the waters of the Turawa Reservoir, measured in 2018, were (µg L− 1): mean < 0.092, min. < 0.04, max. 0.25.
Investigations into the sanitary condition of Turawa Reservoir water, conducted in 2019–2021, indicate a significant probable number of exceedances of coliform bacteria (CBN) in 2020–2021 (Table 6). Exceedances of faecal enterococci (FEN) and large numbers of heterotrophic microorganisms (TNB) were also recorded in 2020. In 2019, there were no exceedances of CBN and FEN. The problem occurring in the last two decades is evidenced by local announcements and press reports based on the results of tests of Turawa Reservoir waters conducted by the District Sanitary and Epidemiological Station in Opole, with examples: July 2005 – CBN exceedance; July 2010 – CBN and FEN exceedances; July 2015 – CBN exceedance.
The presented results indicate that, over the past two decades, the quality of Turawa Reservoir waters has improved in terms of biogenic indicators and cadmium concentration, which for many years was one of the chemical indicators that classified the chemical status of the reservoir waters as being below the “good” status. Still of concern are the biological indicators: IFPL and IO, as well as pH, indicating frequent exceedances of the limit values for water quality class II of surface water type 0, namely dam reservoirs. This problem is reported by 22. Frequent exceedances of indicators of sanitary status are also of concern. The ionic composition of F−, Cl−, Br−, SO42−, Na+, K+, Ca2+ and Mg2+ and the salinity level of the reservoir are not a problem.
Extensive data on, among other things, the natural characteristics of the catchment area, the reservoir and its surroundings, GPR studies of the reservoir basin, studies of the distribution and composition of bottom sediments, groundwater investigation, and studies of the ecological status of the reservoir carried out in 2003 and 2004 were collected in a monograph, published in Polish, titled “The ecological status of Turawskie Reservoir: Assessment of the ecological condition of Turawskie Reservoir in order to develop measures for its improvement” 42.
4.2. Identification of water pollution sources in the Turawa Reservoir
Analysis of literature data indicates two main sources of pollution of the reservoir waters: polluted waters of the Mała Panew River 43 and bottom sediments accumulated since the 1940s in the basin of the Turawa Reservoir 44,45. For many years the Mała Panew River basin water has had exceedances of limit values for many indicators, including nutrients and heavy metals. The catchment area includes forested, urbanised, agricultural and industrial areas 26, and extends, as mentioned, to the Upper Silesia area. The maps in Fig. 9 show examples of the results of measurements of eutrophic indicators carried out in 2004–2007, as well as exceedances of limit values in the assessment of the ecological status in 2013–2015. It is important to note the pollution of the Graniczna Woda watercourse, whose waters through the Stoła watercourse enter the Mała Panew River. Numerous exceedances of oxygen indicators, biogenic indicators and heavy metal concentrations were recorded in the Border Water in 2013–2015 46.
Our research carried out in 2019–2021 indicates sites where there was an increase in the relative concentrations of oxygen and nutrient indicators in the waters of the Mała Panew River (Figs. 4a and 4b): an above average increase in the CODCr indicator near Kalety (Fig. 2a, site 3), an above average increase in the BOD5, CODCr, PO4-P and TP indicators at the inflow of the Table into the Mała Panew River (Fig. 2a, site 8), and an increase, well above average, in the concentrations of various forms of nitrogen near Zawadzkie (Fig. 2a, sites 11–13). Higher concentrations of heavy metals, especially Zn and Pb, were also recorded in the waters of the Mała Panew River, following the inflow of the waters of the Stoła River towards the reservoir (Fig. 8a). The Stoła River, or rather its tributary Graniczna Woda, was identified as a major source of pollution in the waters of the Mała Panew River in 2013–2015 (Fig. 9). A study was conducted in 2000–2002, which showed that the bottom sediments (surface fraction < 1 mm) of the Stoła River and its tributary Graniczna Woda contained up to 3 mg g− 1 Cd, 0.9 mg g− 1 Cu, 20 mg− 1 Pb and 30 mg− 1 Zn 47. Based on an analysis of the results of studies of heavy metal concentrations in sediments carried by the Mała Panew River into the floodplain, supported by dendrochronological studies, a conjecture was made that, in 1960–1985, the waters of the Mała Panew River may have been among the heaviest metal-polluted waters in Europe 48.
The presented data indicate that, for many decades, pollution carried with the waters of the Mała Panew River has been a serious burden on the Turawa Reservoir ecosystem. However, own studies conducted in 2019–2021 indicate that the quality of the waters of the Mała Panew River has significantly improved. Based on the results of the studies, it can be concluded that, in the waters of the Mała Panew River, the average values of the studied indicators (Tables 2, 4 and 5), with the exception of CODCr and NH4-N, are comparable or lower than those of the waters of the Turawa Reservoir. The reservoir is not burdened by the waters of the Libawa River, which reached a good ecological status in 2013–2015 22. Our studies (Fig. 4e, 4f and 6) indicated the relatively good quality of Libawa waters.
The second mentioned source of pollution of the reservoir waters is the accumulation of sapropel bottom sediments, and the pollutants and toxic substances accumulated in them. In a study conducted in 2004 44, pesticides, polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and a number of toxic heavy metals, such as Cd, Hg and Pb, were identified in the bottom sediments of Turawa Reservoir. The presence of heavy metals in the bottom sediments of the reservoir is also confirmed by other authors. In 2003–2004, the range of concentrations (min.–max.) of heavy metals in sapropel sediments that had accumulated in the eastern and north-eastern parts of the reservoir were: Cd 0.35–0.40 mg g− 1, Pb 0.60–0.70 mg g− 1, Zn 7–8 mg g− 1 42, average concentrations of heavy metals were determined in the bottom sediments in the sapropel zone as: Cd 0.280 mg g− 1, Cr 0.038 mg g− 1, Cu 0.105 mg g− 1, Mn 0.940 mg− 1, Ni 0.037 mg g− 1, Zn 4.77 mg g− 1 45. Large amounts of TP were also identified in the sapropel zone in 2008 in sapropel sediments: 1.8 ± 0.6 mg g− 1 49. Studies of the radioactive distribution of 137Cs in the bottom sediments of the reservoir have also been conducted 50. The Turawa Reservoir is located in the area of the so-called Opole Anomaly, where, after the Chernobyl nuclear power plant accident, a relatively large deposition of this radionuclide was recorded for the area of Poland 51.
Figure 10a shows the results of our studies of the horizontal distribution of concentrations of oxygen indicators (Fig. 4e), biogenic indicators (Fig. 4f) and biogenic ions determined by ion chromatography (Fig. 6c). Based on the results 52, the distribution of increments of heavy metal concentrations in samples of biosorbents exposed in the waters of Turawa Reservoir in 2019–2021 is shown in Fig. 10b. The images do not reflect the scale of absolute concentration. They indicate the approximate location of sites where the measured concentrations were higher than the average values determined for the measurement points indicated in Fig. 2b (oxygen indicators BOD5 and CODCr and biogenic indicators TN and NH4-N) and Fig. 3 (biogenic ions NO2−, NO3−, PO43− and NH4+ and heavy metals Ni, Zn, Cd and Pb). Isolines with the percentage of sapropel sediments in the total volume of accumulated bottom sediment are also marked on the reservoir plan (the study was conducted in 2003–2004 42.
The results presented here confirm the impact of two sources of pollution of the reservoir waters: the primary source, through the waters feeding the reservoir, and the secondary source, which is the sapropel bottom sediments accumulated over many decades. However, it is important to note the unfavourable oxygen indicators, which are mainly found in the north-eastern part of the reservoir. It can be assumed that they are the result of biochemical processes involving living and dead organic matter. This is observed by the large increase in the north-eastern part of the reservoir in the indicators BOD5 and CODCr, that took place in September, during the final period of the cyanobacteria bloom (Fig. 5c). Such a phenomenon was not observed in the feed waters (Fig. 5a). Moreover, in the part of the reservoir in question (Fig. 6c), there was an increase in the concentration of nutrient ions during late summer and early autumn (Fig. 6d). Also, such changes did not occur in other parts of the Turawa Reservoir or in the waters feeding the reservoir. In the second half of summer, a significant increase in the concentration of hydroxyl anions was observed in the reservoir waters (Fig. 7).