1. Introduction
Phosphorus (P) and nitrogen (N) are important components of aquatic ecosystems. They are closely linked to the carbon cycle, determining the primary production and the mineralization of organic matter in water. Considered the main cause of eutrophication, these macronutrients are vital in the management of riverine and lacustrine ecosystems [
1,
2,
3,
4].
Eutrophication is a global-scale environmental issue responsible for water quality deterioration, toxic algal bloom, anoxia, and loss of biodiversity [
5,
6,
7]. Inputs of N and P from natural sources are generally low and comprise P release from weathering rocks, leaching from soils and decomposed plant material, atmospheric deposition of N compounds, and biological N fixation through cyanobacteria [
4,
8,
9]. The causes of eutrophication are primarily anthropogenic—processes of industrialization, urbanization and, to a considerable extent, intensification in agriculture. Other sources of anthropogenic inputs of nutrients to riverine systems are municipal and industrial wastewater, runoff from urban areas, increased atmospheric deposition of NO
x due to burning of fossil fuels, agricultural fertilizers, increased soil leachate and erosion due to tillage [
9,
10,
11,
12].
In recent years, special measures have been taken to mitigate nutrient loads in rivers, specifically the improvement of wastewater treatment, banning phosphates in detergents or implementation of good management practices in agriculture [
13,
14,
15]. However, their effects on water quality are often modest due to N and P accumulated in soils, groundwater, lakes and reservoirs, especially in floodplains. Although zones adjacent to rivers have proven to be especially effective in trapping nutrients, the processes occurring there have not been closely examined [
4,
16,
17]. Therefore, riverine system management should be supported by research aimed at an in-depth investigation of floodplains, including river channels, riparian zones, wetlands and water bodies.
Small floodplain reservoirs are one of the least-studied elements of floodplains. Downing et al. [
18] estimated that globally there are about 277 million lakes with a surface area <0.01 km
2, which accounts for 16.5% of global lake area, however, due to their small size, these reservoirs tend to be underestimated and poorly examined. Many of those water bodies are located within the floodplains, in the close vicinity of the river and play an important role in retaining and transforming N and P compounds. The first source of nutrients is allochthonous input. Seasonal river water level fluctuations lead to the periodic connection and disconnection of the river channel and floodplain reservoirs, thus causing the exchange of chemically different water sources. Sediments of floodplain reservoirs become an N and P sink for the river, contributing to the improvement of river water quality [
19]. Moreover, floodplain lakes trap nutrients and sediments from surface runoff, generally from agricultural sources, preventing it from entering the river [
20,
21]. Particular forms of autochthonous N and P depend on the conditions in the water body. Aerobic conditions favor nitrification (transformation of NH
4+ into NO
3−). In anaerobic conditions, NO
3− is transformed into N
2 in the denitrification process. Phosphorus, on the other hand, is adsorbed by sediment particles, however, it could also be released again to the water column and act as the internal P source [
22,
23].
The described processes take place both in large and small floodplain lakes, however, the latter are more sensitive to nutrient enrichment. Owing to a higher sediment-area–water-volume ratio than large lakes, the release of nutrients from the sediment into the water is more possible [
24]. Moreover, small reservoirs are more susceptible to climate change. Increasing mean air temperature causes a direct increase in surface water temperatures, intensification of evaporation and eutrophication processes, decrease in oxygen and increase in pollutant concentrations in water bodies [
25,
26].
Small floodplain lakes accumulate N and P from the river, surface runoff and primary production [
27]. On the other hand, they are sensitive to nutrient enrichment and the influence of climate changes. During floods, pollutants accumulated in the reservoir water and sediments could be fed into the river; thereby, the protective role of small lakes as ”river pollutant buffer zones” would be reversed as they could become one of the main diffuse sources of contamination and pose a threat to the river [
28]. Therefore, effective and sustainable international efforts to improve water quality require a profound understanding of complex processes and nutrient cycling within small lakes and reservoirs.
In our study, we determine nutrient concentrations in water and sediments of 10 small floodplain reservoirs, located within the floodplain of the Vistula river, Poland. This type of water bodies is poorly examined, in contrast to oxbow lakes and old riverbeds e.g., [
29,
30,
31]. Small floodplain reservoirs are formed mainly by deep local erosion of materials deposited on the floodplain [
32].
It was assumed that recent climate change, i.e., rising air and water temperature, increased evaporation and drying up of reservoirs, could intensify eutrophication. Therefore, seasonal changes in nutrient concentrations (NH4+, NO3−, total nitrogen TN, PO43− and total phosphorus TP) were measured in water of floodplain reservoirs. In addition, the impact of N and P contents in reservoir sediments, morphological and locations features with respect to influencing the concentrations and spatial horizontal distribution of nutrients within the water bodies.
3. Results and Discussion
The variability of nutrient contents in sediments in reservoirs (res.) 1–10 was high (
Table 1). Water bodies number 8 and 10 displayed the highest difference from the sample, with significantly higher amounts of PO
43− than in sediments of reservoirs 1, 5, 7 and 1, 5, respectively (based on Tukey’s test—the Least Significant Difference (LSD) value). Additionally, in comparison to other reservoirs in res. number 8 the TP levels were 2–2.5 times higher, which was statistically significant difference. Parts S, M and N showed modest variation, with the mean coefficient of variation value about 10%. Although the differences between reservoir sections were not statistically significant, there was a tendency for nutrients to accumulate mainly in the initial and final parts. This spatial distribution of N and P compounds confirmed our assumption that small floodplain reservoirs are subject to similar processes as dam reservoirs. The elevated nutrient content was recorded in the initial parts of these water bodies due to the fresh influx of allochthonous matter. However, most N and P compounds accumulated in their final parts (at the dam), where fine-grained material of strong sorption properties is deposited [
45,
46,
47].
The correlation analysis indicates a strong influence of total organic carbon content and texture on the content of N and P compounds in the sediments (
Table 2). The fine-grained material was characterized by better sorption properties, more effectively binding various compounds, including nutrients. This explains the high content of N and P in res. number 10, whose sediments consisted in almost 50% of silt and clay. Coarse material was found to accumulate less N and P compounds, especially PO
43−. Reservoir morphometric and location characteristics mainly influenced the grain size distribution of the sediments, indirectly affecting their chemical properties. The value of an angle between the floodplain reservoir axis and the river was proven to be a factor influencing the sediment texture [
48,
49,
50,
51], which is reflected in the results of our research: The bigger the angle, the coarser the sediments. The maximum depth of the reservoirs had a similar effect on the texture, in deeper water bodies the share of sand was higher. This translates into a negative correlation between nutrient content and max depth/angle.
The water quality parameters and their seasonal changes in res. 1–10 should be analyzed through the prism of climate change. Between 2017 and spring 2019, the area of the studied small floodplain reservoirs decreased by an average of 37% (
Table 3). In 2019, which had been the warmest year in Poland since the beginning of measurements, the adverse changes in the distribution of precipitation intensified the drying process. In June, as a result of heavy rainfall, the terraces were flooded by the waters carried by the Vistula. However, it did not reduce the rate of reservoir surface shrinkage. After inundation, the water level in the reservoirs quickly returned to the state from before the flood. Consequently, in the period between March and November 2019, the surface of the studied water bodies decreased by 62% on average, with some of them almost completely drying up (
Figure 4).
In terms of water quality, similarly to sediment analysis, res. number 8 and 10 stood out (
Table 4). The high N and P content in the water of res. number 10 could be linked to the texture of its fine-grained sediments. Moreover, it was one of the reservoirs closest to the river (about 200 m), which could also have had an impact on the water chemical composition. Consequently, the content of NO
3− was significantly higher in res. number 10, than in res. number 1, 5 and 6. On the other hand, in the water of res. number 8 there was a notably high amount of NH
4+, 2–11 times higher than in other reservoirs. A probable explanation is that this was the effect of a nearby chemical industrial sewage treatment plant of Grupa Azoty Puławy Fertilisers (nitrogen fertilizer factory).
In all investigated reservoirs the content of N and P compounds (NH
4+, NO
3−, PO
43−, TN and TP) in water was high, indicative of high eutrophication. According to TSI describing trophic states of lakes and reservoirs: Oligotrophic (<40), mesotrophic (40–50), eutrophic (50–90) and hypereutrophic (>90), all investigated reservoirs were hypereutrophic [
43,
44]. The trophic state of the reservoirs is well illustrated by the algal bloom (
Figure 5).
According to Polish [
52] and European Union guidelines [
53], water bodies would be described as “failing to achieve good ecological status” and water quality would be classified as “bad”. The analysis of Statistics Poland [
54,
55] data shows that in the years 2014–2018, the TN load transported by the Vistula river into the Baltic Sea increased by 18,000 tons per year. The high content of TN in small floodplain reservoirs evidences high biomass production. During high water, especially severe floods, nitrogen compounds are washed out from floodplain water bodies, polluting the river and consequently the sea [
56]. Actions aimed at improving surface water quality should consider floodplain reservoirs as an important diffuse nutrient source. This is vital as Poland and other EU countries, despite various water protection measures: Good agricultural practices, erosion reduction, improvement of sewage quality, reduction of detergent usage, fail to achieve good surface water quality and reduce nutrient loads exported into the Baltic Sea [
57,
58,
59], which was the aim of the European Union’s Water Framework Directive [
53].
The concentration of most investigated water compounds (NH
4+, TN and TP) increased during the growing season (
Figure 6), which was caused by drought. The drying up of the reservoirs was a key factor in the seasonal changes in water quality. A significant loss of water led to a reduction in the area of the water bodies, which was confirmed by strong correlations between the percentage reduction in the surface of reservoirs and the increase in the levels of NH
4+ (r = 0.793), TN (r = 0.744) and TP (r = 0.631) in the water during the year (the significance limit of a correlation coefficient based on Student’s
t-test, r = 0.632,
p = 0.05,
n = 10). The problem of deteriorating water quality during droughts is not limited to small floodplain reservoirs, as it applied similarly to rivers and other water bodies [
60,
61,
62,
63].
There were, however, exceptions: NO
3− and PO
43− with the highest concentrations during summer (
Figure 6). It could have been related to the flooding of the terraces in June—after the spring sampling and before the summer measurements. The Vistula is a heavily polluted river, which exports nearly half of the total phosphorus load into the Baltic Sea [
33]. Moreover, in 2014–2018, the load of NO
3− carried by the Vistula into the Baltic Sea increased by 8,000 tons per year [
54,
55]. Phosphates come primarily from insufficiently treated municipal and industrial wastewater, while highly soluble and mobile nitrate is transported to the river from agricultural areas. The summer increase in the content of PO
43− and NO
3− in the studied water bodies resulted from the exchange of water between the reservoirs and the river, which carried high amounts of phosphates and nitrates. This assumption is supported by significant correlations between the spring–summer change in PO
43− and NO
3− concentrations in the reservoirs and the reservoirs-river distance, r = −0.762 and r = −0.696, respectively (the significant correlation at
p = 0.05,
n = 10). The mean concentration of NO
3− and PO
43− in the water of investigated river section in the spring–summer period was 0.8 and 0.2 mg·L
−1, respectively, which was more than in the water of reservoirs. Additionally, it should be noted that during periods of intense rainfall and high flows, amounts of nutrients carried by the river could be increased [
64]. After the inundation of the terraces in early June, the highest increase in PO
43− and NO
3− concentrations was recorded in the reservoirs closest to the Vistula. When the terraces are flooded by the river, the reservoir–river water exchange occurs more intensively near the main riverbed. Along with an increasing distance from the river, the influence of flooding water, and thus the content of phosphates and nitrates deposited by the river, decrease [
65]. The lower content of these elements in autumn indicates changes in their form. Floodplain lakes are considered effective tools in trapping phosphorus [
66,
67], therefore, excess PO
43− from water might have been bound by sediments.
The contents of nutrients in water were positively correlated with each other (
Table 5), only the content of TP did not show any relationship with other compounds. The nutrient correlations between the sediments and water were different (
Table 6). The content of TP and PO
43− in the sediments was strongly correlated with the content of NH
4+ and NO
3− in the water. The total organic carbon accumulated in the sediments also had a significant influence on the water chemical properties, it increased the content of most compounds, especially NO
3− and PO
43−. Furthermore, the sediment texture significantly influenced the content of nutrients in the water. In reservoirs with coarse-grained sediments, nutrient concentration in water was lower; considering the reservoirs of fine-grained sediments, especially with a high share of clay, more nutrients were noted in the water, especially NO
3− and PO
43−. In small floodplain water bodies, the sediment-area–water-volume ratio is high, which enhances the correlations between water and sediments. It was evident in the relationship between water nutrient content and sediments texture. Moreover, high temperature accelerates sorption of phosphate by sediments [
24,
68]. The year 2019 was the warmest in Poland since 1950 [
38], which additionally affected PO
43− water-sediment transformations.