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Article

Assessment of the Impact of Industrial and Municipal Discharges on the Surface Water Body Status (Poland)

by
Marta Wiesner-Sękala
* and
Beata Kończak
Central Mining Institute, Department of Water Protection, Plac Gwarków 1, 40-166 Katowice, Poland
*
Author to whom correspondence should be addressed.
Sustainability 2023, 15(2), 997; https://doi.org/10.3390/su15020997
Submission received: 9 December 2022 / Revised: 28 December 2022 / Accepted: 29 December 2022 / Published: 5 January 2023
(This article belongs to the Special Issue Environmental Pollution and Monitoring)
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Abstract

:
Due to potential pressure from industrial and municipal activities, urban water bodies are at risk of not achieving the environmental objectives of the Water Framework Directive (WFD) by 2027. This study comprised the quality assessment of water body “Kłodnica do Promnej (bez)” under a strong anthropogenic influence. The main potential sources of pollution in the catchment were identified and the related characteristic contaminants were analysed. The obtained values of pollutants were compared with the limit values for surface waters from Regulation (Journal of Laws 2021, item 1475). The results confirmed that the analysed water body located in highly urbanized area is characterized by poor water quality and chemical status below the good status. The main threat to the aquatic environment is high salinity associated with the presence of mine water discharges. Moreover, the priority substances, such as Cd, Ni and Pb, exceeded the environmental quality standards values (EQS) in most of the designated measurement points. Due to the fact that water ecosystems do not constitute stand-alone structures, but are included in a wider socio-ecological system, the implementation of an integrated approach to characterizing the existing status of the water bodies and estimating the risk posed to the aquatic ecosystem is a crucial element of the catchment management process in the context of the provisions of the WFD.

1. Introduction

All Member States of the European Union (EU) are obligated to protect inland surface waters, transitional waters, coastal waters and groundwater according to the common framework established by Water Framework Directive 2000/60/EC (WFD) [1]. In accordance with WFD [1], the basic environmental goal for all surface waters is to achieve, at minimum, a good water status for natural surface water bodies or good ecological potential and good chemical status for artificial and heavily modified water bodies. This goal should have been achieved by 2015 and, in justified cases, by 2021 or 2027 or as soon as natural conditions permit after 2027 (Guidance Document, 2003) [2]. Europe’s water is under pressure due to increasing economic activities, growing population and urbanization process. There is a high probability that the objective of good status for all EU waters by 2027 is far from reach [3,4].
Bearing in mind the challenges posed by the Water Framework Directive, within the following study the quality assessment of surface water body “Kłodnica do Promnej (bez)” was performed based on the physico-chemical analysis. Specific types of contaminants and related potential sources have been identified and considered during the selection of measurement points. Finally, the classification of the surface water body was conducted in accordance with limit values included in Regulation (Journal of Laws 2021, item 1475) [5]. A significant threat is the salinity of the freshwater ecosystems, which requires further research to reduce ecological consequences in future. The problem is complex because the mining activities causing the salinity of rivers in the region provides economic and social benefits for human well-being. This study is especially important due to the low complexity of the current State Environmental Monitoring (SEM) for assessing the impact of potential sources of pollution on aquatic ecosystems. In Poland, the assessment is conducted for the water body status of rivers, lakes, transitional and coastal waters within the State Environmental Monitoring. Evaluation of the quality of surface waters in the framework of the SEM is based on the Act of 20 July 2017 on Water Law (Journal of Laws of 2021 item 2233 as amended) [6] which implements the requirements of Water Framework Directive. The main scope of conducted monitoring is to provide knowledge about the water status to take appropriate actions for the improvement and protection of water bodies. The undertaken activities should ensure protection against eutrophication and protection against industrial pollution, including salinity and hazardous substances for the aquatic environment. The scope and method of research and the criteria for the assessment of water status are specified in the regulations to the Water Law Act [6] among others Regulation of the Minister of Infrastructure of 25 June 2021 on the classification of ecological status, ecological potential and chemical status and the method of classification of the state of surface water bodies and environmental quality standards for priority substances (Journal of Laws 2021, item 1475) [5].
The Kłodnica river is an example of a river located in the Upper Silesian Coal Basin (USCB) which is the strongest anthropogenically transformed area of Poland [7]. The Kłodnica river is draining the central part of the Silesian Voivodeship and is a receiver of domestic and industrial sewage [8]. The water body “Kłodnica do Promnej (bez)” JCWP PLRW60006116159, analysed within the following article is covered by operational monitoring which is conducted for waters at risk of failing to achieve the environmental targets. The scope of the analysis conducted within the operational monitoring is limited to basic biological and physicochemical indicators which are recognized in diagnostic monitoring as problematic.
The characteristics of rivers located in the USB catchment area has been the subject of many previous studies [9,10,11]. According to the literature data about 35 coal mines are still active [12]. The main receivers of discharged mine water are: Oder, Ruda with Nacyna, Bierawka, Kłodnica with Bytomka, Czarna Przemsza, Pogoria, Brynica, Biała Przemsza with Bobrek, Przemsza, Mleczna, Gostynia and Vistula [13]. Most of the rivers have been transformed by anthropogenic influences. For example, Bytomka river which is right-bank tributary of the Kłodnica river have undergone such strong transformations that their sources are now impossible to identified and it is assumed that its beginning is a ditch carrying urban and industrial sewage [9]. It is similar in the case of the Czerniawka river (right-bank tributary of the Kłodnica river) which, at the beginning of its course, is a receiver of domestic and economic sewage from the city of Ruda Śląska [14].

2. Materials and Methods

2.1. Characteristic of Study Area

The Kłodnica river is located in Upper Silesian Coal Basin (USCB) which is characterized by a very high population density and the presence of many branches of industry, mainly the hard coal mining industry. The Kłodnica river is a right-bank tributary of the Oder River. The sources of the Kłodnica river are located in the Murckowskie forests (Katowice), the river flows through a densely populated industrial part of the Silesian Voivodeship collecting municipal and industrial sewage and underground water from Katowice, Ruda Śląska, Zabrze and Gliwice. This part of the Kłodnica catchment is highly transformed by anthropogenic influences and the riverbed is sewered and concreted almost on the whole length of its course to prevent water from escaping to mining excavations [9]. Due to the industrial nature of the catchment, significant loads of pollution are discharged into the river, resulting consequently in high salinity, the presence of biogenic substances and heavy metals [15]. The detailed characteristic of the Kłodnica river has been described in multiple previous publications [16,17,18,19,20].
In accordance with Odra River basin Management Plan [21], constituting the basic planning document for water management within the Water Framework Directive (WFD), the water body PLRW60006116159 “Kłodnica do Promnej (bez)” is located in the water region of the upper Odra in the Odra basin. The analysed water body is classified as a carboniferous upland stream with fine-grained substrate on loess and loess-like sediments. The status of this natural water body was assessed as having a bad status. The document indicates that the analysed section of the Kłodnica river is threatened by failure to achieve environmental objectives; therefore, the derogation caused by the impact of anthropogenic activity related to the occurrence of natural resources and the industrial nature of the area and the lack of technical possibilities to limit this influence has been designated.
The surface water analysis in terms of physicochemical, chemical and biological elements including priority substances is performed by competent authority—The Voivodeship Inspector for Environmental Protection. The National Hydrological and Meteorological Service is responsible for assessment of hydrological and morphological elements and delivering the results of these analyses to the minister responsible for water management, Polish Waters, the competent body of the Environmental Protection Inspection, and the competent bodies for nature protection. The surface water body monitoring is performed at measurement-control points allowing for the assessment of their condition. However, in the case of some surface water bodies located in heavily urbanized areas, it is insufficient to determine only one representative measurement-control point to identify potential sources of pollution and to estimate their emissions.
According to the latest results of the classification of quality indicators of rivers water bodies and dam reservoirs in 2020 in the Silesian Voivodeship presented on the Chief Inspectorate of Environmental Protection website, the water body “Kłodnica do Promnej (bez)” has been classified with low ecological potential and as having a chemical status below good [22]. One representative measurement-control point Kłodnica river—below the mouth of Jamna stream—was designated for this water body as a part of the state monitoring. The water body was classified above class 2 due to the high concentration of chemical elements such as dissolved substances, sulphates, chlorides, ammonium nitrogen, ni-trite, phosphate phosphorus (V), total phosphorus. Due to the low amount of phyto-benthos, the water was classified as class 4 (Table 1). For the priority substances and substances particularly harmful to the aquatic environment the limit value was exceeded in the case of the cadmium and its compounds, fluoranthene, lead and its compounds, nickel and its compounds, benzo (a) pyrene (Table 2). Due to the identified exceedances the chemical status of the analysed water body was identified as having a status of below good and water class as >1.

2.2. Sampling and Physicochemical Analyses

Surface water samples for physicochemical analysis were collected during five sampling campaigns which took place 10 October 2016, 28 November 2016, 3 June 2017, 30 May 2017 and 4 October 2017 in the selected measurement points which are characterized in the table below (Table 3).
The location of the measurement points was selected to assess the potential impact of the identified contaminant sources, such as mine water discharges (coal mine “Wujek”—point no. 2—and Halemba—point no. 6) and wastewater discharges (wastewater treatment plant “Panewniki”—point 2—and “Halemba Centrum”—point no. 7). The location of representative control-point for operational monitoring corresponds to measurement point no. 5 (The Kłodnica river below the mouth of the Jamna stream) within which measurements were conducted in the study. The location of measurement points is presented in the following figure (Figure 1).
The measurement of parameters was conducted partly in the field using a measuring probe MULTI 3630 IDS (pH, water temperature, conductivity, total dissolved solids and dissolved oxygen) and partly in the laboratory using the appropriate techniques characterized in the table (Table 4). For the determination of metal concentration, the material collection procedure included field filtration of surface water samples through a 0.45 μm membrane filter into 150 mL containers containing concentrated nitric acid. Samples for analysis were delivered to the laboratory on the day of collection.

2.3. Classification Method of the Water Body Sections

Based on the concentrations obtained from laboratory analyses, the average (arithmetic mean) and maximum values were calculated for selected parameters for each measurement point in Microsoft Excel 2010. The average values were calculated based on data from five sampling campaigns, although not all parameters were measured every time. Nevertheless, this is more comprehensive due to the number of measurement points and the list of analysed parameters than state monitoring. Subsequently, the calculated average and maximum values were compared with the national limit values (Journal of Laws 2021, item 1475) [5]. The classification of water body based on selected pollutants which are related to the type of industrial activities perform in the Kłodnica catchment has been made. Limit values for the selected parameters were extracted from the regulation presented in the table (Table S1 in Supplementary Materials) for defined type of the water body [5]. According to the State Environmental Monitoring (SEM) the water body ”Kłodnica do Promnej (bez)” has been classified as carbonate upland stream with fine-grained substrate on loess and loess-like rocks.
In the case of priority substances, the comparison of average and maximum concentration to existing limit of Annual Average Environmental Quality Standards (AA-EQS) and Maximum Allowable Concentrations Environmental Quality Standards (MAC-EQS), was performed, whereas for physicochemical elements and substances that are particularly harmful, the average concentration was compared to the limit values from mentioned above regulation [5]. This approach allowed to assess the scale of the threat posed to the ecosystem by industrial and municipal discharges. Within the study the following parameters were analysed in surface water samples: pH, Zn, Cu, Hg, Cd, Ni, Pb, BOD (biochemical oxygen demand), COD Cr, (chemical oxygen demand), TN (total nitrogen), TP (total phosphorus), TSS (total suspended solids), Cl−, SO42−, Ca, Mg, electrical conductivity, temperature, DO (dissolved oxygen), TDS (total dissolved solids) and TH (total hardness).
The methodology implemented within the study is summarized in the flow chart below (Figure 2).

3. Results and Discussion

3.1. Basic Physicochemical Indicators

In the case of general parameters characterizing surface waters, such as pH, it can be observed that the analysed surface water samples are mostly alkaline and fall within the class I of limits for indicators characterizing acidification (limit values: 7.2–7.9). Only in the measurement point no. 1, the average value (6.93 pH) in range of a slightly acidic character was identified (Table 5). The first measurement point is located near the source section of the Kłodnica river in the southern part of the city of Katowice, in the territory of the Murckowskie forests. The Kłodnica sources are placed in the Landscape-Nature Protected Complex “Źródła Kłodnica”, which was established to protect the headwaters area of the Kłodnica river, which is a right tributary of the Oder. This river section is characterized by its small amount of water and how it dries periodically. The results of the study showed the neutral or alkaline character of the discharges into the Kłodnica river. According to Masindi et al., in 2017 [23], the negative impact on the environment is particularly related to the acid mine water containing toxic compounds which are a result of leaching hazardous chemicals from the surrounding bedrock.
The temperature of surface water at individual measurement points showed variation. At the measurement points located below mine water discharges, a significant increase in river water temperature was observed (16.5 °C in point no. 2 and 18.6 °C in point no. 6). It stems from the fact that the temperature of water pumped from the mines of the Upper Silesian Coal Basin (USCB) ranges from 13 °C to 25 °C [24]. However, the average results obtained for temperature of the Kłodnica river range in the I class of indicators characterizing thermal conditions (≤22 °C). The average concentration of total suspended solids (TSS) showed a growing trend along the river sections. A particularly significant increase below the mouths of the Jamna stream (34 mg/L in point no. 5) and below the discharge point from “Halemba Centrum” wastewater treatment plant (38 mg/L in point no. 7) was identified. From the measurement point no. 4 to point no. 7 the total suspended solids concentration in surface water exceeded the limits for class II (≤16.4 mg/L). The observed increase in TSS in surface water samples confirms that pumped out mine water contains suspended solids. In practice, pumped mine water is directed to sediments pounds designed for a two day hydraulic retention time before it is released into the receiver [25]. The total suspended solids (TSS) concentration in water discharged to the environment should not exceed 35 mg/dm3 [25].

3.2. Oxygen Conditions and Biogenic Substances Indicators

There are two wastewater treatment plants (STP) located in the area of the study. Both of them—“Panewniki” (point no 2) and “Halemba Centrum” (point no. 7)—are mechanical-biological treatment plants that meet the European Union (EU) standards. The pressure from the treated wastewater discharged into the river appears through elevated parameters, often exceeding limit values for class II, especially in case of BOD (≤3.8 mg O2/L) and COD-Cr (≤30 mg O2/L) (Table 6). The highest average values for COD-Cr were observed in measurement point no. 5 (31 mg O2/L) and no. 7 (31.67 mg O2/L). In the same points, the limit values for BOD for the class II were exceeded (point no. 5–3.9 mg O2/L, point no. 7–4.03 mg O2/L) (Table 6). COD-Cr and BOD are a basic indicator of the degree of organic pollution in water bodies [26,27]. The COD-Cr indicates higher levels of oxidizable organic matter contributing to a lower amount of DO. Dissolved oxygen in water is a main indicator of water quality and reflects the river metabolic changes [28]. For DO the potential below good was detected in point 1 which reflects the state of the river. At the source of the Kłodnica river water flows poorly (nearly stands still) and has a form of small spills with very low water level. The correlation between the increased chemical oxygen demand and the low concentration of dissolved oxygen in the water is visible in point 1 (Table 6). TP and TN are the major parameters indicating surface water eutrophication process and water quality degradation [29]. Potential below good based on the limit value for TN (≤6.9 mg/L) has not been identified at all points of analysed water body. Good potential (≤4.6 mg/L) has been observed in points: no. 2, no. 5 and no. 7. The location of measurement point no. 2 and no. 7 are situated below discharge points from wastewater treatment plants which explains the slightly elevated values of TN indicator. According to the European Environmental Agency’s data [30] for period 2017–2019, the highest percentage of rivers with average nitrate concentrations exceeding 5.6 mg NO3-N/L were observed in United Kingdom (26%) and France (24%). Furthermore, countries, such as Switzerland, Belgium, Lithuania, Czech Republic, Denmark and Germany, were characterized by a large percentage (over 25%) of sites with concentrations exceeding 3.6 mg NO3-N/L. However, the study of Hamerla and Kończak (2021) [31] showed that the higher concentration of nitrogen in water body is related to the pressure from the dispersed sources, such as agriculture and atmospheric deposition. In addition, elevated phosphorus loads play an important role in the deterioration of water quality and may pose a threat to aquatic organisms. Monitoring the flows of total phosphorus (TP) from the catchment has particular importance for the welfare of river ecosystem. The main sources of the supply load of phosphorus in rivers are dissolved or particle-bound phosphorus from sewage/industrial effluents (point sources) and agricultural areas (dispersed sources) [31,32]. Despite the improvement of river water quality, a significant number of European surface water bodies do not meet the TP concentration levels required to achieve good ecological status under the Water Framework Directive [33,34]. In the case of analysed water body “Kłodnica do Promnej (bez)” the potential below good (limit value: ≤0.35 mg/L) was identified in the measurement point no. 2, which is located below the wastewater treatment plant “Panewniki” (0.45 mg/L). Slightly increased concentration of TP, classifying the analysed sections of the Kłodnica river into category of good potential (limit value: ≤0.15) were identified in points no. 3, 4, 5 and 7. It can be assumed that the decrease in TP concentration in point no. 6 results from dilution process with water from Jamna stream and discharged water from the coal mine “Halemba”.

3.3. Indicators Characterizing Salinity

The major threat to the aquatic ecosystem identified in the following study is related to the high salinity of the river (Table 7).
The exception is measurement point 1, which is not exposed to the impact of coal mine discharges. All analysed indicators related to salinity (Cl, SO4, Mg, Ca, TDS, TH and conductivity) exceeded the permissible values for class II from regulation [5] many times, which means that, apart from the first river section (from point no. 1 to point no. 2), the analysed water body has a status potential below good. The most exceeded values for salinity indicators relate to chloride and conductivity (Figure 2). Electrical conductivity is related to the concentration of ions in the water which come from dissolved salts and inorganic materials such as alkalis, chlorides, sulphides and carbonate compounds [35]. While the limit for class I is ≤ 374 µS/cm [5], some studies have demonstrated that value 300 µS/cm is a benchmark to protect aquatic insect communities in streams [36]. Within our study the highest average conductivity value was 8 438 µS/cm (point no. 6). According to Qin et al. (2020) [37] at moderate water temperature (20–25 °C) and salinity (35 psu), a population of Prymnesium parvum (Haptophyta) may develop forming toxic blooms throughout the world, resulting in large fish die-offs. Moreover, they discovered that the toxicity was reduced significantly at higher or lower temperatures and salinities and was greatly enhanced when ambient nutrients were deficient. Additionally, salinity usually refers to the accumulation of ions, which causes an increase in electrical conductivity and/or total dissolved solids (TDS) [38]. However, electrical conductivity is not equal to TDS, but can be treated as a useful field indicator for monitoring process [39]. The concentration of TDS results from organic salts, organic matter and other dissolved materials in water. The high TDS average concentration in analysed measurement points is correlated with high ions concentration (Cl, SO4, Mg and Ca). The highest peak concentration of all salinity indicators, especially of chlorides and sulphates is visible in sections below discharges from coal mines “Wujek” (Cl—1732.40 mg/L, SO4—234.2 mg/L) and “Halemba” (Cl—2404 mg/L, SO4—532.80 mg/L). The banks of the Kłodnica river are formed from material from hard coal mine “Halemba” in section located near the points no. 4 and no. 5. Salts, mainly chlorides and sulphates, may be leached in these areas which is visible in average concentration of salinity indicators despite the lack of mine water discharge in this area. Subsequent wet and dry deposition increases the value of salinity indicators as in the example of point no. 4, where values for conductivity and chlorides are exceeded many times.
The number of exceedances of limit values for class II is presented in the Figure 3.
The highest number of exceedances was observed below the discharge point from the coal mine “Halemba” (point no. 6). The limit values were exceeded as follow for chlorides (35.4 times) > conductivity (15.3 times) > magnesium (5.3 times) > sulphates (4.8 times), TH (2.9 times) > calcium (2.2 times) > TDS (1.7 times). Similar results were obtained by Jabłońska examining the influence of salinity on the water quality of the Goałwiecki stream and its environmental status, a river flowing through Upper Silesia under the pressure of mine waters discharges [40]. The increased salinity in freshwater ecosystem is correlated with reduction in biodiversity including species or functional richness connected with changes in aquatic community composition [41]. Due to the different sensitivity of freshwater organisms to salinity stressors, a change in the aquatic ecosystem may occur not only directly (change in species composition) [42], but also indirectly, such as a change in species interactions [43]. There is scientific evidence that ions such as magnesium, potassium and sulphate are more toxic to freshwater organisms than sodium or chloride [44]. The limit value for class II for chloride is ≤ 68.0 mg/L according to Regulation (Journal of Laws 2021, item 1475) [5]. This value is exceeded 35.4 times in point no. 6 and 25.5 times in point no. 2. It should be noted that the values determined for the analysed water body refer specifically to carboniferous upland stream with fine-grained substrate on loess and loess-like sediments. For comparison, according to Canadian water quality guidelines (for the province of Ontario) for chronic and acute toxicity limits for chlorides are 120 mg/1 and 640 mg/L, respectively [45]. In the US, the established chronic value is 230 mg/L, while acute toxicity is 860 mg/L [46,47]. The information about safe levels of sulphates is scarcer. According to the literature data, the concentration of sulphates in rivers range from 0 to 630 mg/L [48]. For example, based on the procedures typically used in the development of provincial WQGs in British Columbia (Canada), the toxicity limit values for sulphate including the water hardness separate for soft (10–40 mg/L), moderately hard (80–100 mg/L) and hard water (160–250 mg/L) were developed. The designated values for sulphate concentration were 129, 644 and 725 mg/L, respectively, within the procedure based on species sensitivity distribution (SSD), and 75, 625 and 675 mg/L, respectively, within the safety factor approach [49]. It has been scientifically proven that increasing water hardness and chloride concentrations cause a significant decrease in sensitivity of freshwater organisms to sulphate [48,49].
The average values of salinity indicators obtained within the study confirm that anthropogenic activity influence the state of aquatic environment in this highly urbanized region. Exceeding the physicochemical parameters is reflected in the poor biodiversity of the analysed water body and in the state monitoring results indicated poor ecological status where the biological elements was assessed as class 4 (see Table 1). The summary assessment of the physicochemical parameters in our study indicates that these elements are below class II (potential below good), which is confirmed in the results of state monitoring. The obtained results correspond with the analysis presented by Zgórska et al., in 2016 [50], where the risk caused by high salinity mine water discharges in the USCB was assessed. The study showed that mine water discharges to the Przemsza river elevated the salinity indicators. Concentrations for chloride range from 40.32 [mg/L] to 729.91 [mg/L] and for sulphate from 98.97 [mg/L] to 680.77 [mg/L].
Taking into account the requirements of the WFD [1] and existing exceedances of water parameters, some bioremediation systems may be considered to mitigate the impacts of salinity. The treatment systems, such as reactive barriers, bioreactors and constructed wetlands, are widely used around the world to remove contaminants (e.g., removal efficiency for sulphate ranges from 0% to 70%) [48].

3.4. Priority Substances and Substances Particularly Harmful

The second identified threat to the water body “Kłodnica do Promnej (bez)” is heavy metals, especially Ni, Pb and Cd, in concentrations exceeding the designated AA-EQS (Table 8) and MAC-EQS (Table 9). In all analysed points the average content of metals follows the order Ni > Pb > Cd > Hg. In accordance with the recommendations of Directive 2013/39/EU [51], in the case of Cd, Pb, Hg and Ni, the bioavailability of these metals should also be considered after the determination of TH, pH, COD and other parameters concentration which affect the bioavailability of metals. Appropriate modelling of bioavailability is also recommended. The chemical status assessment of Cd and its compounds was based on taking into account the TH values which establishes the EQS values expressed in five hardness classes (class 1: <40 mg CaCO3/L, class 2: 40 to <50 mg CaCO3/L, class 3: 50 to <100 mg CaCO3/L, class 4: 100 to <200 mg CaCO3/L and class 5: ≥200 mg CaCO3/L). According to these designated levels the values of EQS for the measurement point refers to class IV (AA-EQS = 0.15 µg Cd/L) in measurement point no 1, while for the rest corresponds to the value of class V (AA-EQS = 0.25 μg/L). The exceedance of Cd was observed for average concentration in measurement point no. 1, 4, 5 and 7. In case of Ni, the average concentration exceeded the EQS (AA-EQS = 4 μg/L) in all of analysed measurement points. While for Pb (AA-EQS= 1.2 μg/L) the average concentration was exceeded only in sources section of Kłodnica river (point no. 1) and at the closure point of waterbody “Kłodnica to Promnej (bez)” (point no. 7). Moreover, at these points (no. 1 and no. 7) the limit values for three heavy metals (Cd, Ni and Pb) were exceeded which indicates the chemical status of water body below good (Table 8).
Analysis of the maximum values of the selected heavy metals showed that in almost all analysed points of the river the MAC-EQS values were exceeded except point no. 2 (Table 9).
The results showed that the content of heavy metals in the Kłodnica river basin increased significantly. This confirms the high impact of drainage waters and wastewater from mining regions on the quality of surface waters. The same results presented by Gabrielyan et al. (2018) [52] demonstrated that the concentration of heavy metal ions was significantly changed due to anthropogenic impact disturbing the geochemical balance of the Voghji River in China. Furthermore, the highest value for Cd (9.3 μg/L) and Ni (10 μg/L) was detected in measurement point no. 1, while for Pb in measurement point no. 7 (4 μg/L). High concentrations of metals at the point no. 1 may result from the fact that the section has a form of springs where the water is stagnant in scarce amount. There may occur the chemical leaching process when precipitation from rainfall or snow melt infiltrates through ground and dissolves or desorbs metals from the solid material. The point no. 1 is located in an environmentally protected area. It is advisable to extend the soil tests at this point in order to determine the sources of increased Cd concentrations in the Kłodnica river.
Zn and Cu are included in the group of quality indicators from the group of substances particularly harmful to the aquatic environment (specific synthetic and non-synthetic pollutants) according to the regulation Journal of Laws 2021, item 1475 [5]. The average concentration did not exceed the limit values for class I and II from regulation [5] (Table 10).
The observed increased concentration of heavy metals should be related to the industrial impact from coal mines, sewage and all activities resulting from human urbanization process. A similar study was conducted in China, where, in 2018, Ji et al. [53] studied the impact of mine water at 11 sites along the Yongding river. It was observed that concentrations of heavy metals increase in the following order: supernatant water < pore water < sediment. Pb and Zn contamination dominates in pore waters. Cu and Zn are mainly associated with the reducible fraction and Cr, Ni and Pb are strongly bound to the residual fractions [53].
The high content of heavy metals such as Hg, Cd, Pb, Cr, Cu, Zn and Ni in mine water is caused by the process of dissolving of heavy metals present in coal and their release into waters [54].
Heavy metals enter surface water in liquid forms and insoluble salts or complexes are formed with water components (e.g., carbonate, sulphate and humic organic substances) [55]. Upon entering water, heavy metals accumulate in the sediments where the remobilization process takes place. The risk they pose to freshwater organisms is due to the fact that they are non-transformable to less toxic compounds and they are non-biodegradable [56]. According to the literature data, saline water that also contains heavy metals is discharged from Silesian mines [56]. The high concentration of heavy metals, especially in sediments, was observed in the Przemsza river in the catchment area where mines are located. High concentrations of Cd, Zn and Pb that exceed the values of the geochemical background more than a hundred times were observed in the riverbed of the Biała Przemsza [56].
The assessment process presented above was based on comparison values for selected heavy metals with the aim to establish limit values and does not include bioavailability correction with the exception of Cd. In the case of Ni and Pb, further detailed analysis of the parameters affecting bioavailability is necessary. For this purpose, it is possible to use interactive tools based on Biotic Ligand Models (BLM) allowing to determine local EQS or PNEC (Predicted No-Effect Concentration) values depending on physicochemical parameters of surface waters (pH, dissolved organic carbon (DOC) and Ca), which affects the bioavailability of metals. This approach takes into account the interaction between metals and aquatic organisms [57]. According to the comparative analysis of existing tools constituting simplified BLM, it is recommended to use them as tools supporting the surface water monitoring process in the context of the WFD [58,59,60,61]. As it was presented in the article on the Kłodnica river [18,19], local values of EQS calculated based on simplified BLM tools are much higher than values recommended in Directive and therefore the exceedances were not observed in the case of Pb and Ni. It can be predicted that a similar situation may also occur in the presented case due to the fact that the concentration of DOC, Ca and pH are relatively high. The correlations documented thus far prove that waters with relatively high dissolved organic carbon concentrations may reduce the toxicity of metals [62]. Considerations put forward by the Hommen and Rüdel (2012) [63] based on the performed study on simplified BLM tools are that the calculated local quality standards increase with DOC growth, while the higher Ca concentrations does not increase the bioavailability of metals. The performed study made it possible to assess the chemical status below good which coincides with the assessment of state monitoring (see Table 1). However, to evaluate the potential toxicity of heavy metals, tools that take into account the bioavailability of metals and allow the determination of local limit values should be used. The toxic effect of saline waters was also studied on another river that receives mine waters—the Bolina river, which flows through the highly industrialized and urbanized part of Upper Silesia. The study showed that the increase in salinity in the lower course of the river caused by the discharge of mine water into the Bolina River, was reflected in the decrease in the median density, the number of rotifer taxa and the Shannon-Wiener H0 index [64].
The results showed that there is a slight variation between individual measurement points which is especially visible between the first and last points closing the analysed water body. Having an understanding of the poor surface water quality of the analysed river water body, it can be assumed that the achievement of good water body status by 2027 is not feasible due to the existing industrial and municipal economic pressures in the catchment area. The concentrations of physicochemical elements relating to potential contamination from mines and waste water treatment plants indicates a significant impact on aquatic environment.

4. Conclusions

This study included a quality assessment of an urban water body located in a highly urbanized region placed under strong and specific pressures from industry and the municipal economy. Selected types of pollutants are closely related to the existing human economic activity connected with the presence of natural resources and the industrial character of the catchment area. Poor water quality has been identified as a result of increased salinity parameters, most of them exceeded the limit values for class II (i.e., Cl−, SO42−, Ca, Mg, conductivity, TDS and total hardness). Exceeding the limit values was also observed in the case of BOD and COD-Cr parameters, which indicates an increased concentration of organic substances in surface waters. Exceeded EQS values for Ni, Pb and Cd, classified as priority substances, contributed to the poor chemical status of the water body. Therefore, the approach based on the use of interactive tools that make it possible to estimate the bioavailability of heavy metals and determine local limit values is a key element of the catchment management process in highly urbanized areas. In light of the WFD and its daughter directives, practical implementation of European regulations with regard to chemical pollution has faced big challenges. Taking into account the existing impact of anthropogenic activities on the status of the water body “Kłodnica do Promnej (bez)” and the lack of technical possibilities to limit these impacts from coal mines on aquatic environment, it can be concluded that fulfilment of ecological ambitions by 2027 is unlikely. The assessment of the potential pressure is particularly important for catchments where many potential sources of municipal and industrial pollutions are located. It should be concluded that assessment methods considering only the aquatic pollutant concentration are insufficient for monitoring highly anthropogenic transformed river water bodies. It is insufficient to be limited to the location of one state monitoring point (“the Kłodnica river below the mouths of the Jamna stream”) and the measurement of selected types of pollutants when the aim is to recognize potential sources of pollution in the catchment area and to estimate the risk posed by related contaminants. Water ecosystems do not constitute stand-alone structures but are included in a wider socio-ecological system, therefore the implementation of an integrated approach to characterizing the existing status of the surface water bodies and estimating the risk posed to the aquatic ecosystem is a crucial element of the catchment management process.
The main challenge is to catch the balance between environmental, social and economic aspects connected with freshwater contamination by various polluters. It should be taken into account that activities causing freshwater salinization are related to economic and social benefits. Therefore, the catchment management process should be adopted to specific surface water bodies under the influence of strong anthropopressure from industry and municipal economy. The environmental monitoring should be improved to be able to provide reliable data on potential threats and existing exceedances of surface water parameters. Moreover, limits from the regulation should not be the only determinant, but the interactive tools based on BLM models and algorithms and biotests should complement the monitoring. The improvement of water parameters in rivers can be mainly achieved by implementation of technical solutions (discharge management system) and bioremediation techniques (constructed wetlands, bioreactors and permeable reactive barriers) adjusted to nature and/or type of pollutant, which may be considered as cost-effective and self-maintaining in the long-term perspective.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/su15020997/s1. Table S1: Limits of surface water quality indicators from Journal of Laws 2021, item 1475 relating to river water bodies classified as carbonate upland stream with fine-grained substrate on loess and loess-like rocks [5].

Author Contributions

The authors confirm contribution to the paper as follows: Conceptualization: M.W.-S. and B.K.; methodology: M.W.-S.; validation: M.W.-S.; formal analysis: M.W.-S. and B.K.; data curation: M.W.-S.; writing—original draft preparation: M.W.-S.; writing—review and editing: M.W.-S. and B.K.; visualization: M.W.-S. and B.K., supervision: M.W.-S. and B.K., project administration: M.W.-S. and B.K.; funding acquisition: M.W.-S. All authors have read and agreed to the published version of the manuscript.

Funding

This study was supported by the grant no 11311117-343 as a part of statutory research founded by Polish Ministry of Science and Higher Education.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data upon which this paper is based are available from the authors upon request.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Location of measurement points (point no. 1–no. 7) on the water body “Kłodnica do Promnej (bez)” and measurement sections (I–VI).
Figure 1. Location of measurement points (point no. 1–no. 7) on the water body “Kłodnica do Promnej (bez)” and measurement sections (I–VI).
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Figure 2. Methodology implemented within the study.
Figure 2. Methodology implemented within the study.
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Figure 3. Number of exceeding the limit values for salinity indicators for class II from Journal of Laws 2021, item 1475 [5].
Figure 3. Number of exceeding the limit values for salinity indicators for class II from Journal of Laws 2021, item 1475 [5].
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Table
Table 1. Classification of water body “Kłodnica do Promnej (bez)” according to regional data concerning classification of river water bodies available on the Chief Inspectorate of Environmental Protection website [22].
Table 1. Classification of water body “Kłodnica do Promnej (bez)” according to regional data concerning classification of river water bodies available on the Chief Inspectorate of Environmental Protection website [22].
Water ClassPhysicochemical ElementsChemical ElementsBiological ElementsOther
Class 1temperature, dissolved oxygen, pHtotal organic carbon, total nitrogen, volatile phenols–phenolic index, petroleum hydrocarbons–oil index, anthracene, benzo (b) fluoranthene, benzo (k) fluoranthene, Benzo (g, h, i) terylene
Class >1hydromorphological observations
Class 2biochemical oxygen demand (BOD), Kjeldahl nitrogen, nitrate, barium, boron, zinc, copper
Class >2Conductivity at 20 °Cdissolved substances, sulphates, chlorides, ammonium nitrogen, nitrite, phosphate phosphorus (V), total phosphorus
Class 4phytobenthos
Table
Table 2. Concentrations of priority substances according to regional data concerning classification of river water bodies available on the Chief Inspectorate of Environmental Protection website [22].
Table 2. Concentrations of priority substances according to regional data concerning classification of river water bodies available on the Chief Inspectorate of Environmental Protection website [22].
Priority SubstancesCadmium and Its CompoundsFluorantheneLead and Its CompoundsNickel and Its CompoundsBenzo(a)piren
Value [average (av), maximum (max)]avmaxavmaxavmaxavmaxavmax
Concentration [µg/L]0.290.940.01270.02051.32.54.612.80.002230.00492
Table
Table 3. Characterization of measurement points.
Table 3. Characterization of measurement points.
No. of Measurement PointLocation of Measurement Point
1Below the source section of the Kłodnica river.
2The Kłodnica river above the mouth of the Ślepiotka stream and below the discharge point of the coal mine “Wujek” and the wastewater treatment plant “Panewniki”.
3The Kłodnica river below the mouths of the Ślepiotka stream.
4The Kłodnica river above the mouth of the Jamna stream.
5The Kłodnica river below the mouths of the Jamna stream.
6The Kłodnica river below the discharge point of the coal mine “Halemba”.
7The Kłodnica river below the discharge point of the wastewater treatment plant “Halemba Centrum”, at the closure point of waterbody Kłodnica to Promnej (bez).
Table
Table 4. Methods used to measure individual parameters in surface water samples.
Table 4. Methods used to measure individual parameters in surface water samples.
Analysed ParameterMeasurement MethodInternational StandardsThe Range of Measurements
Cu2+ICP-MS (inductively coupled plasma mass spectrometry)PN-EN ISO 17294-2:20062–2000 μg/L
Ni2+ ICP-MS (inductively coupled plasma mass spectrometry)PN-EN ISO 17294-2:20062–2000 μg/L
Pb2+ICP-MS (inductively coupled plasma mass spectrometry)PN-EN ISO 17294-2:20061–2000 μg/L
Cd2+ ICP-MS (inductively coupled plasma mass spectrometry)PN-EN ISO 17294-2:20060.05–2000 μg/L
Zn2+ ICP-MS (inductively coupled plasma mass spectrometry)PN-EN ISO 17294-2:20062–2000 μg/L
Hg2+CV-AAS (cold vapor atomic absorption spectroscopy)PN-EN 1483:2007
PN-EN 12338:2001
US EPA 7473		0.05–10,000 μg/L
Ca2+ICP-OES (inductively coupled plasma optical emission spectrometry)PN-EN ISO 11885:20090.02–20,000 mg/L
Mg2+ICP-OES (inductively coupled plasma optical emission spectrometry)PN-EN ISO 11885:20090.012–12,200 mg/L
Cl−IC (ion chromatography)PN-EN ISO 10304:20090.28–177,300 mg/L
SO42−IC (ion chromatography)PN-EN ISO 10304:20090.10–10,000 mg/L
Total suspended solids (TSS)weightPN-EN 872:2007 + Apl:20072–10,000 mg/L
Chemical oxygen demand COD-Cr (COD)spectrophotometricPN-ISO 15705-200510–200,000 mgO2/L
Biochemical oxygen demand (BOD)electrochemicalPN-EN 1899-1:2002
PN-EN 1899-2:2002		without dilution:
0.5–6 mg/L O2
after dilution:
3–6000 mg/L O2
Total Nitrogen (TN)High Temperature Combustion and Infrared Detection(IR)/chemiluminescentPN-EN 12260:20040.5–2500 mgN/L
Total Phosphorus (TP)ICP-OES (inductively coupled plasma optical emission spectrometry)PN-EN ISO 11885:20090.01–5000 mg/L PO4
0.0003–158 mmol(r)/L
0.003–1630 mg/L P
0.007–3740 mg/L P2O5
Total hardness (TH)from calculations based on the Ca and Mg, alkalinity measurements--
Table
Table 5. Average concentration of basic physicochemical indicators in selected measurement points of water body “Kłodnica do Promnej (bez)” compared to the limit values from Journal of Laws 2021, item 1475 [5].
Table 5. Average concentration of basic physicochemical indicators in selected measurement points of water body “Kłodnica do Promnej (bez)” compared to the limit values from Journal of Laws 2021, item 1475 [5].
Measurement PointTemp.
[°C]		TSS
[mg/L]		pH
1—Below the source section of the Kłodnica river.13.010.906.93
2—The Kłodnica river above the mouth of the Ślepiotka stream and below the discharge point of the coal mine “Wujek” and the waste water treatment plant “Panewniki”.16.510.487.67
3—The Kłodnica river below the mouths of the Ślepiotka stream.15.89.247.71
4—The Kłodnica river above the mouth of the Jamna stream.16.021.007.92
5—The Kłodnica river below the mouths of the Jamna stream.16.134.007.77
6—The Kłodnica river below the discharge point of the coal mine “Halemba”.18.633.007.95
7—The Kłodnica river below the discharge point of the waste water treatment plant “Halemba Centrum”, at the closure point of waterbody Kłodnica to Promnej (bez).18.238.207.68
Class Imaximum potential
Class IIgood potential
Failure to meet the limits of Class IIpotential below good
Note: the backcolor indicates the classification of individual parameters.
Table
Table 6. Average concentration of oxygen conditions and biogenic indicators in selected measurement points of water body “Kłodnica do Promnej (bez)” compared to the limit values from Journal of Laws 2021, item 1475 [5].
Table 6. Average concentration of oxygen conditions and biogenic indicators in selected measurement points of water body “Kłodnica do Promnej (bez)” compared to the limit values from Journal of Laws 2021, item 1475 [5].
Measurement PointBOD
[mg O2/L]		COD-Cr
[mg O2/L]		DO
[mg O2/L]		TN
[mg N/L]		TP
[mg P/L]
1—Below the source section of the Kłodnica river.1.1830.005.550.900.01
2—The Kłodnica river above the mouth of the Ślepiotka stream and below the discharge point of the coal mine “Wujek” and the waste water treatment plant “Panewniki”.2.3324.338.625.170.45
3—The Kłodnica river below the mouths of the Ślepiotka stream.2.5720.678.813.370.35
4—The Kłodnica river above the mouth of the Jamna stream.2.2322.007.832.800.20
5—The Kłodnica river below the mouths of the Jamna stream.3.9031.008.696.300.23
6—The Kłodnica river below the discharge point of the coal mine “Halemba”.2.8722.678.403.600.10
7—The Kłodnica river below the discharge point of the waste water treatment plant “Halemba Centrum”, at the closure point of waterbody Kłodnica to Promnej (bez).4.0331.678.604.200.20
Class Imaximum potential
Class IIgood potential
Failure to meet the limits of Class IIpotential below good
Note: the backcolor indicates the classification of individual parameters.
Table
Table 7. Average concentration of salinity indicators in measurement points of water body “Kłodnica do Promnej (bez)” compared to the limit values from Journal of Laws 2021, item 1475 [5].
Table 7. Average concentration of salinity indicators in measurement points of water body “Kłodnica do Promnej (bez)” compared to the limit values from Journal of Laws 2021, item 1475 [5].
Measurement PointCa
[mg/L]		Mg
[mg/L]		Conductivity
[μS/cm]		TDS
[mg/L]		TH
[mg CaCO3/L]		SO4
[mg/L]		Cl
[mg/L]
1—Below the source section of the Kłodnica river.41.534.89347.83247.70105.0061.0015.75
2—The Kłodnica river above the mouth of the Ślepiotka stream and below the discharge point of the coal mine “Wujek” and the waste water treatment plant “Panewniki”.107.0843.305656.004654.50393.50234.201732.40
3—The Kłodnica river below the mouths of the Ślepiotka stream.98.8041.155360.004692.50380.50218.801585.40
4—The Kłodnica river above the mouth of the Jamna stream.115.6823.637178.005247.00504.50300.202298.00
5—The Kłodnica river below the mouths of the Jamna stream.115.4860.154353.002669.50509.50319.201318.00
6—The Kłodnica river below the discharge point of the coal mine “Halemba”.143.8088.558438.006940.00684.00532.802404.00
7—The Kłodnica river below the discharge point of the waste water treatment plant “Halemba Centrum”, at the closure point of the waterbody Kłodnica to Promnej (bez).124.2562.406160.004844.00524.50418.201642.00
Class Imaximum potential
Class IIgood potential
Failure to meet the limits of Class IIpotential below good
Note: the backcolor indicates the classification of individual parameters.
Table
Table 8. Average concentration of selected priority substances in measurement points of water body “Kłodnica do Promnej (bez)”. Concentration of Cd, Ni and Pb compared to the AA-EQS values from Journal of Laws 2021, item 1475 [5].
Table 8. Average concentration of selected priority substances in measurement points of water body “Kłodnica do Promnej (bez)”. Concentration of Cd, Ni and Pb compared to the AA-EQS values from Journal of Laws 2021, item 1475 [5].
Measurement PointHg
[μg/L]		Cd
[μg/L]		Ni
[μg/L]		Pb
[μg/L]
1—Below the source section of the Kłodnica river.0.033.356.931.73
2—The Kłodnica river above the mouth of the Ślepiotka stream and below the discharge point of the coal mine “Wujek” and the waste water treatment plant “Panewniki”.0.030.124.540.79
3—The Kłodnica river below the mouths of the Ślepiotka stream.0.030.184.540.83
4—The Kłodnica river above the mouth of the Jamna stream.0.030.375.420.86
5—The Kłodnica river below the mouths of the Jamna stream.0.030.265.060.78
6—The Kłodnica river below the discharge point of the coal mine “Halemba”.0.030.215.680.71
7—The Kłodnica river below the discharge point of the waste water treatment plant “Halemba Centrum”, at the closure point of waterbody Kłodnica to Promnej (bez).0.030.374.661.57
Good chemical statusnot exceeding the AA-EQS value
Chemical status below goodfailure to meet the AA-EQS value
Note: the backcolor indicates the classification of individual parameters.
Table
Table 9. Maximum concentration of selected priority substances in measurement points of water body “Kłodnica do Promnej (bez)” compared to the MAC-EQS values from Journal of Laws 2021, item 1475 [5].
Table 9. Maximum concentration of selected priority substances in measurement points of water body “Kłodnica do Promnej (bez)” compared to the MAC-EQS values from Journal of Laws 2021, item 1475 [5].
Measurement PointHg
[μg/L]		Cd
[μg/L]		Ni
[μg/L]		Pb
[μg/L]
1—Below the source section of the Kłodnica river.0.039.3010.003.00
2—The Kłodnica river above the mouth of the Ślepiotka stream and below the discharge point of the coal mine “Wujek” and the waste water treatment plant “Panewniki”.0.030.205.601.25
3—The Kłodnica river below the mouths of the Ślepiotka stream.0.030.276.301.25
4—The Kłodnica river above the mouth of the Jamna stream.0.030.427.001.50
5—The Kłodnica river below the mouths of the Jamna stream.0.030.446.401.20
6—The Kłodnica river below the discharge point of the coal mine “Halemba”.0.030.366.501.25
7—The Kłodnica river below the discharge point of the waste water treatment plant “Halemba Centrum”, at the closure point of waterbody Kłodnica to Promnej (bez).0.031.105.804.00
Good chemical statusnot exceeding the MAC-EQS value
Chemical status below goodfailure to meet the MAC-EQS value
Note: the backcolor indicates the classification of individual parameters.
Table
Table 10. Average concentration of selected substances particularly harmful in measurement points of water body “Kłodnica do Promnej (bez)” compared to limit values from Journal of Laws 2021, item 1475 [5].
Table 10. Average concentration of selected substances particularly harmful in measurement points of water body “Kłodnica do Promnej (bez)” compared to limit values from Journal of Laws 2021, item 1475 [5].
Measurement PointZn
[μg/L]		Cu
[μg/L]
1—Below the source section of the Kłodnica river.442.53.28
2—The Kłodnica river above the mouth of the Ślepiotka stream and below the discharge point of the coal mine “Wujek” and the waste water treatment plant “Panewniki”.54.82.72
3—The Kłodnica river below the mouths of the Ślepiotka stream.70.22.72
4—The Kłodnica river above the mouth of the Jamna stream.89.02.88
5—The Kłodnica river below the mouths of the Jamna stream.83.03.12
6—The Kłodnica river below the discharge point of the coal mine “Halemba”.75.23.38
7—The Kłodnica river below the discharge point of the waste water treatment plant “Halemba Centrum”, at the closure point of waterbody Kłodnica to Promnej (bez).54.82.94
Class I and IImaximum potential
Failure to meet the requirements of class I and IIpotential below good
Note: the backcolor indicates the classification of individual parameters.
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Wiesner-Sękala, M.; Kończak, B. Assessment of the Impact of Industrial and Municipal Discharges on the Surface Water Body Status (Poland). Sustainability 2023, 15, 997. https://doi.org/10.3390/su15020997

AMA Style

Wiesner-Sękala M, Kończak B. Assessment of the Impact of Industrial and Municipal Discharges on the Surface Water Body Status (Poland). Sustainability. 2023; 15(2):997. https://doi.org/10.3390/su15020997

Chicago/Turabian Style

Wiesner-Sękala, Marta, and Beata Kończak. 2023. "Assessment of the Impact of Industrial and Municipal Discharges on the Surface Water Body Status (Poland)" Sustainability 15, no. 2: 997. https://doi.org/10.3390/su15020997

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