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Article

Pollution Assessment and Spatial Distribution of Heavy Metals in Surface Waters and Bottom Sediments of the Krzna River (Poland)

by
Mariusz Kluska
* and
Joanna Jabłońska
Faculty of Sciences, Siedlce University, 3 Maja 54, 08-110 Siedlce, Poland
*
Author to whom correspondence should be addressed.
Water 2024, 16(7), 1008; https://doi.org/10.3390/w16071008
Submission received: 3 March 2024 / Revised: 23 March 2024 / Accepted: 28 March 2024 / Published: 30 March 2024
(This article belongs to the Section Soil and Water)
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Abstract

:
Due to their toxicity, lack of bioaccumulation and biodegradability, and ease of binding to sediments, heavy metals are considered the main pollutants of rivers. It is, therefore, necessary to control and monitor these pollutants. The present study analyzed the Krzna River, which flows in southeastern Poland and has an outlet to the Bug River. Over much of its length, the Bug River forms Poland’s border with Belarus, while its origin is in Ukraine. The main purpose of the conducted research was a qualitative and quantitative analysis of selected heavy metals, i.e., Ni, Pb, Zn, Cd, and Cu, in bottom sediments and surface waters of the Krzna River. The secondary objectives were to evaluate the level of contamination of the studied matrices and identify the sources of pollution. Eighty samples of water and bottom sediments from the Krzna River were collected for the analysis. Due to the varying distribution of metals under the influence of changes in temperature, precipitation, and humidity, the samples were collected in May and August 2023. The average cadmium content in the sediments studied was the same in both May and August, at 0.6 mg/kg. In contrast, the nickel content of the sediments ranged from 4.6 to 6.1 mg/kg in May and from 4.8 to 6.8 in August. Only nickel and cadmium of the five heavy metals tested were present in amounts exceeding the geochemical background value. Analysis of the results indicates that only a minimal amount of heavy metals remain dissolved in the surface waters, and the remainder contaminates the sediments. The average concentrations of metals in the studied bottom sediments and surface waters were as follows: zinc > lead > nickel > copper > cadmium. The content of metals in the studied sediments was not high, but at the same time, their presence above the geochemical background indicates anthropogenic human activity. Any changes in hydrodynamic conditions and various environmental factors may result in the re-release of heavy metals contained in sediments into surface waters.

1. Introduction

Water pollution is now a global problem [1,2,3]. It is estimated that by 2100, access to clean water is likely to be a problem for up to 5.5 billion people. Water occupies seventy percent of the Earth’s surface. Day by day, rivers, seas, and oceans are becoming increasingly polluted. The increasing concentration of heavy metals in the last years is one of the most troublesome aspects of environmental contamination. They are classified as pollutants that pose a particularly serious threat to human health. The content of heavy metals in bottom sediments and surface waters is an important indicator of the state of the aquatic environment [4,5,6,7,8,9,10,11].
In nature, there are different types of ecosystems depending on their characteristics and main environment. One of them is the aquatic ecosystem. In this case, the main environment is water. The liquid phase is bordered by a gaseous phase, i.e., atmospheric air, and a solid phase, i.e., the bedrock covered by a layer of bottom sediments. Therefore, many pathways for the migration of pollutants are considered, including surface water. Heavy metals are released into the aquatic environment from natural and anthropogenic sources. The main natural sources are rock volcanic eruptions, weathering, and soil erosion. Large amounts of heavy metals are also generated by mining, metallurgy, agriculture, sewage sludge disposal, or the burning of fossil fuels [12,13,14,15,16,17].
Heavy metals are considered major pollutants in the aquatic environment. They are of great concern because of their high toxicity and persistence, high bioaccumulation, and lack of biodegradability [18,19,20,21,22,23,24]. Their content varies depending on the bottom of the water body and the water column. Over the years, it has been shown that approximately 90% of heavy metals in the aquatic environment are found specifically in fine sediments. During the self-purification processes of surface water, soluble forms of heavy metals migrate into the bottom sediments. This is associated with sedimentation and sorption processes. As a result, water quality is improved, but at the same time, the content of heavy metals in bottom sediments increases [4,25,26,27,28]. Environmental conditions, such as pH, electrical conductivity, and oxidation reduction potential change, result in heavy metals re-entering the water, resulting in secondary water pollution. They are then transported for hundreds of kilometers until they are deposited in bottom sediments and temporarily immobilized. Since heavy metals enter the aqueous phase very easily, the concentration level of heavy metals in bottom sediments should be considered a very sensitive indicator of the purity of the aquatic environment [29,30,31,32].
The toxicity of heavy metals in water depends on the form of a specific metal compound, as well as its degree of oxidation. Metals and semimetals are very easily released from bottom sediments. Most often, a decrease in the pH of water leads to the dissolution of carbonates and hydroxides, in which metal ions are displaced by hydrogen ions. An increase in the water salinity causes a shift in the sorption isotherm toward a higher pH, which can lead to the formation of soluble metal–anion complexes. The change in redox potential is also important. This is associated with changes in the forms of metal binding in the solid phase and a decrease in pH. This primarily results in an increase in the mobility of metals. Heavy metal concentrations also depend on the seasons. Intense rainfall, among other things, contributes to soil erosion, leading to the release of heavy metals into the water. Precipitation and sedimentation are the dominant processes that cause metals to accumulate in bottom sediments. In addition, acid rain causes a sharp drop in the pH of water, which also contributes to a sharp increase in the concentration of metals in the water [33,34,35,36,37,38,39].
This study was conducted to determine whether the waters and bottom sediments deposited in the subject reservoir pose a potential threat to the environment. The research was conducted in a protected area. For the first time, the degree of contamination of bottom sediments by pollution indicators (Cf) was assessed and compared with values according to the Hakanson scale. An analysis of the literature data indicates that the number of studies conducted in the area is negligible. To date, no publications have been found on the state of the water in this river.
The main purpose of this study was to analyze the content of heavy metals (Pb, Zn, Ni, Cd, Cu) in the bottom sediments and surface waters of the Krzna River, assess the degree of pollution, and identify the sources of pollution and their migration pathways. News of the content of metals in the samples may be applied in the future to accurately determine the characteristics of the aquatic environment and management aimed at reducing pollution.

2. Materials and Methods

2.1. Study Area and Sample Preparation

Eighty samples (bottom sediment and surface water) from the Krzna River were collected for this study. The river is situated in eastern Poland and is a left tributary of the Bug River with a length of 120 km (Figure 1). Its basin area is 3353 km2. The Krzna River is formed from two streams flowing out of the Łuków Forest, Krzna Północna, and Krzna Południowa. The latter is assumed to be the origin of the Krzna River. The Krzna River flows into the Bug River northwest of the city of Terespol. Over its considerable length, the Bug River forms Poland’s international border with Ukraine and Belarus. Water levels are strongly dependent on the Bug River. The average flow near the mouth of the Bug River is 10.5 m3/s. The Krzna River has three small left tributaries and four right tributaries. Three cities are located on the Krzna River: Łuków, Międzyrzec Podlaski, and Biała Podlaska, from which treated wastewater is discharged. The Krzna Południowa River valley features the Zimna Woda retention basin, meadows, allotments, a boulevard, a park, a stadium, and a sewage treatment plant. The built-up areas are surrounded by farmland and wasteland. A large part of the area through which the Krzna River flows is protected as a reserve. The Krzna River valley is also included in the Natura 2000 network. A total of 750 plant species, including numerous protected species, occur in the Bug River Landscape Park. About 290 species of birds, mammals, amphibians, reptiles, and fish have also been confirmed in the area. One of the biggest threats to the nature of the Bug River valley is the lowering of groundwater levels. The change from extensive to intensive agriculture is also very unfavorable. The ecological potential of the water in the Krzna River valley is considered to be below good or moderate. This indicates an urgent need for studies to enhance the condition of these waters. Unfortunately, analysis of the literature data reveals that the amount of research carried out in this region is marginal.
Samples were collected on average every 25 km along the Krzna River in May and August 2023. Sampling points are marked on the map with a triangle symbol: Puchacze (S1), Biała Podlaska (S2), Czosnówka (S3), Kijowiec-Kolonia (S4), and Starzynka (S5). A total of 0.2 L of water was collected from each sampling point. The process of sedimentation of suspended solids and the concentration of heavy metals occurred in the riverside zone from which samples were collected for this study. In the case of bottom sediments, samples were taken from under the water surface at a depth of about 10 cm. The samples were divided into two parts. One part from each site was analyzed separately, while the other part was mixed, and one representative test sample of about 1 kg was obtained. The sample thus prepared was also analyzed for the content of the above-mentioned heavy metals.

2.2. Analytical Procedures

The sediment samples collected for this study were first dried at a temperature of 39–40 °C and then passed through a nylon sieve with a mesh diameter of 0.2 mm. Subsequently, 0.5 g of each collected bottom sediment sample was weighed and mineralized using 8 mL of the mixture, consisting of 2 mL of 30% H2O2 and concentrated HNO3. The mineralization process using microwaves was carried out in a closed system. A qualitative and quantitative analysis of the determined heavy metals in the collected samples was conducted simultaneously in four series. After prior filtration, all the analyzed bottom sediment samples were quantitatively transferred to volumetric flasks with a capacity of 50 mL. All tests were carried out by flame atomic absorption spectrometry using a Varian AA-20 spectrometer (Belrose, Australia). In order to verify the analytical results obtained, certified reference material NCSDC 73377 was used, the characteristics of which are presented in Table 1. Five standard solutions of different concentrations were prepared for all the analyzed metals. Then, the accuracy and precision of the analytical method used in this study were evaluated based on the recovery of analytes. The conditions of the analyses conducted using reference material, surface water samples, and bottom sediments are shown in Table 2.
The obtained results were close to the certified value, while the computed measurement error did not exceed 5%. The acidity of the sampled bottom sediments in suspended water, and water was estimated according to the procedure in [40], which complied with ISO 10523:2008 [41].
Samples with particle diameters of less than 200 μm were analyzed for heavy metals in the bottom sediments. Table 3 presents the geochemical criteria taken from the literature for bottom sediments used to classify the analyzed samples.
The most common environmental pollutants are heavy metals. Their content is most often compared to current standards or geochemical background. The content of the metals obtained during this study was compared with the results of other authors and with the regulation currently in force in Poland as of 2019, which is presented in Table 4 [43]. The geochemical criteria were developed by the National Geological Institute and concern the classification of the purity of bottom sediments based on selected trace elements. The Regulation of the Minister of Maritime Affairs and Inland Navigation specifies the requirements to be met by surface water used to supply the public with water for human consumption.
The Hakanson method was used to assess the quality of the sediments studied (Table 5).
When calculating the index of contamination of the bottom sediments with individual heavy metals, the equation Cfi = Ci/C0 was used. The mean content of individual metals analyzed in the bottom sediments was taken as Ci values, while C0 denotes the value of the geochemical background.

3. Results and Discussion

3.1. Analysis of Heavy Metals in the Surface Water

Table 6 and Table 7 show the research results on the Krzna River concerning the content of heavy metals in the analyzed bottom sediment and surface water samples. The following parameters were taken into account: maximum, minimum, arithmetic mean, standard deviation, and median.
Given the geographic location of the studied river, it can be concluded that its sources of pollution are determined by the functioning and expansion of cities and villages located within the catchment area. The main factors affecting the quality of the environment around the Krzna River catchment area include fertilization and plant protection, meat, food, and timber industries, the volume of vehicle traffic, and sewage treatment plants in nearby towns and cities or insufficient performance of the sewage system.
When assessing the level of contamination of the analyzed surface water and bottom sediments of the Krzna River, the obtained results were compared with the geochemical background, i.e., the content of naturally occurring substances in the environment. The determination of the geochemical background is necessary to assess the study area in terms of anthropogenic impacts and whether the effects of these pollutants are already visible. For many years, the assessment of geochemical background proposed by Turekian and Wedephol, which involves factoring in the average content of a given element in the Earth’s crust [46,47,48,49], has been used. The obtained results are combined with the background value calculated locally for Polish sediments and globally, according to the procedure proposed by Bojakowska and Sokolowska [47].
Unfortunately, most countries, along with Poland, of course, are currently experiencing an increasing water deficit. For this reason, the results obtained from the analysis of surface water are compared with the relevant standards for their potential use in various industries. In the case of research on surface waters in Poland, which contain various pollutants deposited in bottom sediments, an assessment is made against the results of studies by other authors and against the applicable Polish, European, and/or world standards. In the present study, a comparison was made with reference to the regulation of the Minister of Maritime Affairs and Inland Navigation, which addresses the requirements for surface waters intended for human consumption [43]. This regulation classifies surface water into three quality categories, with the content of individual heavy metals playing a crucial role in these requirements.
In the studied surface waters of the Krzna River, the cadmium content in May ranged from 0.02 mg/L to 0.07 mg/L, the arithmetic mean was 0.04 mg/L, the median was 0.03, and the standard deviation was 0.26. Similar cadmium levels were obtained in surface water samples collected in August (Table 6). When the obtained cadmium content was compared with the standards under the Ministerial Order (Table 4), it was found that the analyzed waters did not meet the standards and could be defined as substandard waters. Mineral fertilizers containing cadmium are a danger to the environment and living organisms. This threat occurs due to the possibility of cadmium accumulating in the environment and entering the food chain. Its high content in the studied surface waters may be due to the use of mineral fertilizers by farmers and their runoff into the Krzna River since the surrounding land is agricultural.
Figure 2 and Figure 3 show the distribution of the content of the analyzed metals in water and sediment in the samples collected from the Krzna River. The highest concentrations were found for zinc, while the lowest was for cadmium. Higher concentrations compared to cadmium were found for copper, both in the water and bottom sediments. The differences in the pH values and the results along the surveyed river are mainly due to the runoff of mineral fertilizers used by farmers into the river and the discharge of wastewater from the treatment plants of the cities of Łuków, Międzyrzec, and Biała Podlaska.
Results similar to the cadmium content were also obtained for lead in the analyzed surface water. Its content in the studied months was similar and ranged from 3.4 to 8.2 mg/L. A slightly higher average content of this element was recorded in August and was 6.1, while in May it was 5.3 mg/L.
Surface water samples were also analyzed for copper and nickel content. Nickel concentration in May ranged from 1.1 to 1.4 mg/L, with a mean of 1.2 and a median of 1.3 mg/L. In August, on the other hand, nickel content ranged from 1.3 to 1.6 mg/L, with an arithmetic mean of 1.4 and a median of 1.5 mg/L (Table 5). In contrast, the content of copper ranged from 0.5 to 1.4 mg/L in both months, with a mean of 0.9 and a median of 0.8 mg/L in May and 0.8 and 0.6 mg/L, respectively, in August.
Zinc was another element analyzed in the collected samples of bottom sediments and surface water. Excessive amounts of zinc, an essential trace element for organisms in the aquatic ecosystem, cause the deterioration of its metabolism. This element can cause foaming and give water a metallic taste. The zinc concentration in the surface water samples collected from the Krzna River in May ranged from 10.3 to 19.4 mg/L, while the calculated arithmetic mean value was 15.4 mg/L. In August, on the other hand, the content ranged from 11.6 to 19.3 mg/L, with an average of 15.4 mg/L. Median values were similar, i.e., 16.1 in May and 16.5 in August, while the standard deviation was 3.4 and 2.6, respectively. When the results obtained from the study of the Krzna River were compared with the permissible zinc concentration specified in the Ministerial Order of 2019, it was concluded that the analyzed surface waters did not meet the standards and could be defined as substandard waters. Similar conclusions were drawn when comparing the obtained values for the other analyzed heavy metals.

3.2. Analysis of Heavy Metals in Bottom Sediments

The obtained results of the content of selected heavy metals in the studied bottom sediments of the Krzna River are presented in Table 7. Assessment of the degree of sediment contamination with the tested metals was made on the basis of water classification.
The presence of zinc in the sediments is mainly due to human activity. The land around the studied river is agricultural, so the main sources of pollution include liquid fertilizers, stormwater runoff, urban sewage, etc. Zinc can be absorbed by various particles suspended in water and deposited in sediments, which serve as nutrients for bottom organisms.
Zinc concentration in the sediments of the Krzna River ranged from 16.2 to 22.7 mg/kg in May, while in August, it was slightly higher: 16.8–23.5 mg/kg. The arithmetic mean and median in August were also higher and were 19.8 and 19.2 mg/kg of dry sediment, respectively. When the obtained zinc content was compared with the results of the geochemical background in Table 3, it was found that the studied sediments of the Krzna River were slightly contaminated with the heavy metal in question. The median zinc concentration in the analyzed bottom sediments relative to the median for Poland of 73 mg/kg [42] was almost four times lower.
The second heavy metal analyzed was cadmium. Its average content in the studied sediments was the same in both May and August and amounted to 0.6 mg/kg. When the obtained content of this element was compared with the results of other authors, a high similarity was found in relation to the Słupia, Oder, and Supraśl rivers (Table 8). With regard to geochemical criteria (Table 3), the obtained cadmium content does not exceed 1 mg/kg, which means that the analyzed bottom sediments can be classified in the first class of purity. In each of the analyzed sediment samples, regardless of the sampling location along the Krzna River, the characteristic value for the first class of purity was not exceeded. In contrast, the results obtained by other authors for two rivers in Poland exceeded the permissible value for sediments of class I purity (Table 8). The permissible values for cadmium content were also exceeded in rivers of four other countries.
Another metal analyzed was nickel. Its content in the sediments ranged from 4.6 to 6.1 mg/kg in May and from 4.8 to 6.8 in August. The medians for nickel were 5.3 and 5.9 mg/kg (Table 7) and were lower than the European value of 16 mg/kg. With respect to the results of other authors, the obtained nickel content results were significantly lower (Table 8). This analyzed metal shows the ability to form quite stable complexes, such as cationic or chelate.
The copper content was also significantly lower compared to the results obtained by other authors (Table 8). The obtained data show that the mean copper concentration was 3.6 mg/kg in May and 4.5 mg/kg in August (Table 7). The analyzed sediment samples were also characterized by lower lead concentration compared to the results obtained by other authors shown in Table 8.
The content of heavy metals obtained through the analysis of bottom sediments was compared with the results of research by other authors in Poland and Europe, as well as with the geochemical background (Table 3 and Table 8). The results of studies by various authors available in the literature indicate that very different values of heavy metal content were obtained on different continents, at the same time, within quite wide ranges (Table 8) [48,49,50,51,52,53,54,55,56,57,58,59]. This may imply that in many places, the content of metals exceeded the applicable European and/or global standards.
The calculated values of pollution indices for the analyzed metals are presented in Table 9. The degree of pollution (Cd) of the analyzed bottom sediments from the Krzna River was determined by summing up all the pollution index values for the analyzed heavy metals.
When the obtained values of pollution indices (Cf; Table 9) are compared with the values according to the Hakanson scale (Table 5), it can be concluded that the studied sediments are slightly to moderately polluted with the analyzed heavy metals. The metals that classify the studied sediments as slightly contaminated are zinc, lead, and copper, while nickel and cadmium—as moderately contaminated, regardless of the month (date) of sampling.
On the other hand, based on the comparison of the obtained results of this study with the content of heavy metals constituting the geochemical background (Table 3), it can be concluded that the concentrations of the analyzed metals in the sediments of the Krzna River are low and can be classified in class I of purity.

4. Conclusions

The variability of parameters throughout the year, for example, precipitation, humidity, and temperature affect changes in the distribution of metals, which are mainly seasonal, as well as their sources. Small amounts of metals entering the river remain dissolved in the river, while others sink to the bottom and enrich the sediments. The differences in the distribution of the analyzed metals in surface waters confirm the fact that the studied sediments contain long-term contaminants. This fact also points to sediments as a source of analyzed metals in surface waters. The content of some heavy metals, such as cadmium and nickel, allows us to classify the sediments of the Krzna River as moderately polluted. Only two of the five analyzed metals were present in amounts exceeding the geochemical background value. The analysis allows us to conclude that the average concentrations of these metals in the studied bottom sediments and surface waters were as follows: zinc > lead > nickel > copper > cadmium. The amounts of metals found in the analyzed sediments were relatively low, but at the same time, they were sufficient to recognize the negative impact of human activities on the aquatic environment. Changes in environmental factors and conditions can lead to secondary water pollution through the release of metals from bottom sediments.

Author Contributions

Conceptualization, M.K.; methodology, M.K. and J.J.; validation, M.K.; formal analysis, J.J.; investigation, M.K. and J.J.; resources, M.K. and J.J.; data curation, J.J.; writing—original draft preparation J.J. and M.K.; writing—review and editing, M.K. and J.J.; visualization, M.K. and J.J.; supervision, M.K.; funding acquisition, M.K. All authors have read and agreed to the published version of the manuscript.

Funding

This work was sponsored by the Ministry of Education and Science. The funding number is 142/23/B.

Data Availability Statement

Data are contained within the article.

Conflicts of Interest

The authors declare no conflicts of interest.

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Water 16 01008 g001
Figure 1. Sampling area for surface water and bottom sediments with location marked.
Figure 1. Sampling area for surface water and bottom sediments with location marked.
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Water 16 01008 g002
Figure 2. The content of individual metals in the tested waters (blue frame, mg/L) and bottom sediments (green frame, mg/kg) in May, respectively: (a) nickel, (b) cadmium, (c) lead, (d) zinc, (e) copper.
Figure 2. The content of individual metals in the tested waters (blue frame, mg/L) and bottom sediments (green frame, mg/kg) in May, respectively: (a) nickel, (b) cadmium, (c) lead, (d) zinc, (e) copper.
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Water 16 01008 g003
Figure 3. The content of individual metals in the tested waters (blue frame, mg/L) and bottom sediments (green frame, mg/kg) in August, respectively: (a) nickel, (b) cadmium, (c) lead, (d) zinc, (e) copper.
Figure 3. The content of individual metals in the tested waters (blue frame, mg/L) and bottom sediments (green frame, mg/kg) in August, respectively: (a) nickel, (b) cadmium, (c) lead, (d) zinc, (e) copper.
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Table 1. Characterization of NCSDC 73377 reference material after the AAS technique (n = 4, p = 95%, mg/kg).
Table 1. Characterization of NCSDC 73377 reference material after the AAS technique (n = 4, p = 95%, mg/kg).
MetalCertified ValueAAS
Pb8.0 ± 0.57.8 ± 0.4
Ni117 ± 10116 ± 8
Cu84 ± 585 ± 2
Cd0.14 ± 0.020.12 ± 0.03
Zn100 ± 12101 ± 11
Table 2. Analysis conditions: Cd, Pb, Cu, Ni, and Zn by the AAS technique.
Table 2. Analysis conditions: Cd, Pb, Cu, Ni, and Zn by the AAS technique.
MetalDetection Range
(mg/L)		Gap Width
(nm)		Wave Length
(nm)		Accuracy
(%)		Precision
(%)
Pb0.002–101.0217.02010
Cd0.002–40.5228.82010
Ni0.01–100.2232.02010
Cu0.003–50.5324.72010
Zn0.01–151.0213.92010
Table 3. Geochemical background and sediment cleanliness classes with consideration of geochemical criteria [42].
Table 3. Geochemical background and sediment cleanliness classes with consideration of geochemical criteria [42].
MetalPbZnCdCuNi
Class I3020014016
Class II1005003.510040
Class III2001000620050
Class IV>200>1000>6>200>50
Geochemical background (mg/kg DM)1573< 0.575
Table 4. Cleanliness classes of surface waters and the permissible content of selected heavy metals in them according to the 2019 Ordinance [44].
Table 4. Cleanliness classes of surface waters and the permissible content of selected heavy metals in them according to the 2019 Ordinance [44].
MetalI ClassII ClassIII Class
Pb 0.050.050.05
Cd0.0050.0050.005
Ni0.050.050.2
Cu0.050.050.5
Zn355
Table 5. Scale of bottom sediment pollution according to Hakanson [45].
Table 5. Scale of bottom sediment pollution according to Hakanson [45].
PollutionCfCd
Poor<1<8
Moderate1–38–16
Significant3–616–32
Very strong≥6≥32
Notes: Cd—Degree of contamination; Cf—pollution index.
Table 6. Selected statistical data (n = 12) of analyzed indicators in surface waters of the Krzna River.
Table 6. Selected statistical data (n = 12) of analyzed indicators in surface waters of the Krzna River.
ElementMin–Max
(mg/L)		MeanMedianSD
May (pH: 6.73–7.11)
Ni1.1–1.41.21.31.0
Cd0.02–0.070.040.030.26
Cu0.5–1.40.90.80.9
Pb3.4–8.25.36.21.7
Zn10.3–19.415.416.13.4
August (pH: 6.79–7.23)
Ni1.3–1.61.41.50.8
Cd0.04–0.070.050.040. 17
Cu0.5–1.10.80.60.7
Pb5.1–7.96.16.61.5
Zn11.6–19.315.416.52.6
Note: SD—Standard deviation.
Table 7. Basic statistical data (n = 32) on the concentration of analyzed metals in the bottom sediments of the Krzna River.
Table 7. Basic statistical data (n = 32) on the concentration of analyzed metals in the bottom sediments of the Krzna River.
ElementMin–Max
(mg/kg DM)		MeanMedianSD
May (pH: 6.88–7.36)
Ni4.6–6.15.25.31.2
Cd0.4–0.80.60.50.2
Cu1.8–5.33.62.43.1
Pb9.7–15.712.011.81.5
Zn16.2–22.718.817.93.3
August (pH: 6.91–7.34)
Ni4.8–6.86.05.91.4
Cd0.5–0.70.60.60.2
Cu2.3–6.94.54.43.3
Pb10.4–16.312.912.82.2
Zn16.8–23.519.819.23.1
Table 8. Comparison of heavy metal content (mg/kg) in bottom sediments of the Krzna River with the results of heavy metal content in bottom sediments of other rivers.
Table 8. Comparison of heavy metal content (mg/kg) in bottom sediments of the Krzna River with the results of heavy metal content in bottom sediments of other rivers.
Related River
(Country)		Min–MaxRef.
NiCdCuPbZn
Krzna (Poland)4.6–6.80.4–0.81.8–6.99.7–16.316.2–23.5This study
Mojiguaçu (Brazil)8–38n/a9–483–3117–92[47]
Navasota (USA)n/a0.2–0.416–2218–30n/a[48]
Elba (Germany)30–903–662–17440–17213–56[49]
Tisza (Hungary)64–880.2–3.740–13718–304130–570[50]
Morawa (Czech Republic)n/a0.1–4.822–6314–5566–321[51]
Yellow River (China)n/a217–39320–5529–3758–93[52]
Vistula (Poland)n/a1–8n/a28–122180–860[53]
Odra (Poland)7–230.6–0.992–281–23–35[54]
Słupia (Poland)3–140.1–0.72–456–24414–96[55]
Liwiec (Poland)3.3–9.90.2–0.70.7–9.410.4–13.916.4–25.3[56]
Supraśl (Poland)5.4–180.4–1.10.8–163.5–3510–67[57]
Muchawka (Poland)2.3–8.40.1–0.60.7–5.29.8–13.414.4–21.3[58]
Odra River (Poland)37–1083–21.731–29819–343333–2591[59]
Note: n/a—not analyzed.
Table 9. Indicators (Cf) and degree of pollution (Cd) of bottom sediments of the Krzna River.
Table 9. Indicators (Cf) and degree of pollution (Cd) of bottom sediments of the Krzna River.
RiverMonthCfCdPollution
ZincLeadCadmiumNickelCopper
Krzna May0.260.81.161.040.513.77poor
August0.270.861.121.190.654.09poor
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Kluska, M.; Jabłońska, J. Pollution Assessment and Spatial Distribution of Heavy Metals in Surface Waters and Bottom Sediments of the Krzna River (Poland). Water 2024, 16, 1008. https://doi.org/10.3390/w16071008

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Kluska M, Jabłońska J. Pollution Assessment and Spatial Distribution of Heavy Metals in Surface Waters and Bottom Sediments of the Krzna River (Poland). Water. 2024; 16(7):1008. https://doi.org/10.3390/w16071008

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Kluska, Mariusz, and Joanna Jabłońska. 2024. "Pollution Assessment and Spatial Distribution of Heavy Metals in Surface Waters and Bottom Sediments of the Krzna River (Poland)" Water 16, no. 7: 1008. https://doi.org/10.3390/w16071008

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