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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Environ. Sci.</journal-id>
<journal-title>Frontiers in Environmental Science</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Environ. Sci.</abbrev-journal-title>
<issn pub-type="epub">2296-665X</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="publisher-id">874754</article-id>
<article-id pub-id-type="doi">10.3389/fenvs.2022.874754</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Environmental Science</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Variability of Nitrogen and Phosphorus Content and Their Forms in Waters of a River-Lake System</article-title>
<alt-title alt-title-type="left-running-head">Janicka et al.</alt-title>
<alt-title alt-title-type="right-running-head">Nitrogen Phosphorus River-Lake System</alt-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name>
<surname>Janicka</surname>
<given-names>Ewelina</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
<xref ref-type="corresp" rid="c001">&#x2a;</xref>
<uri xlink:href="https://loop.frontiersin.org/people/1676852/overview"/>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Kanclerz</surname>
<given-names>Jolanta</given-names>
</name>
<xref ref-type="aff" rid="aff1">
<sup>1</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Wiatrowska</surname>
<given-names>Katarzyna</given-names>
</name>
<xref ref-type="aff" rid="aff2">
<sup>2</sup>
</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Budka</surname>
<given-names>Anna</given-names>
</name>
<xref ref-type="aff" rid="aff3">
<sup>3</sup>
</xref>
</contrib>
</contrib-group>
<aff id="aff1">
<sup>1</sup>
<institution>Department of Land Improvement, Environmental Development and Spatial Management</institution>, <institution>Faculty of Environmental and Mechanical Engineering</institution>, <institution>Pozna&#x144; University of Life Sciences</institution>, <addr-line>Pozna&#x144;</addr-line>, <country>Poland</country>
</aff>
<aff id="aff2">
<sup>2</sup>
<institution>Department of Soil Science and Land Reclamation</institution>, <institution>Faculty of Environmental and Mechanical Engineering</institution>, <institution>Pozna&#x144; University of Life Sciences</institution>, <addr-line>Pozna&#x144;</addr-line>, <country>Poland</country>
</aff>
<aff id="aff3">
<sup>3</sup>
<institution>Department of Mathematical and Statistical Methods</institution>, <institution>Faculty of Agronomy</institution>, <institution>Horticulture and Bioengineering</institution>, <institution>Pozna&#x144; University of Life Sciences</institution>, <addr-line>Pozna&#x144;</addr-line>, <country>Poland</country>
</aff>
<author-notes>
<fn fn-type="edited-by">
<p>
<bold>Edited by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/1278130/overview">Jiangyu Dai</ext-link>, Nanjing Hydraulic Research Institute, China</p>
</fn>
<fn fn-type="edited-by">
<p>
<bold>Reviewed by:</bold> <ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/584460/overview">Yves Lucas</ext-link>, Universit&#xe9; de Toulon, France</p>
<p>
<ext-link ext-link-type="uri" xlink:href="https://loop.frontiersin.org/people/286293/overview">Yang Yu</ext-link>, Beijing Forestry University, China</p>
</fn>
<corresp id="c001">&#x2a;Correspondence: Ewelina Janicka, <email>ewelina.janicka@up.poznan.pl</email>
</corresp>
<fn fn-type="other">
<p>This article was submitted to Freshwater Science, a section of the journal Frontiers in Environmental Science</p>
</fn>
</author-notes>
<pub-date pub-type="epub">
<day>21</day>
<month>04</month>
<year>2022</year>
</pub-date>
<pub-date pub-type="collection">
<year>2022</year>
</pub-date>
<volume>10</volume>
<elocation-id>874754</elocation-id>
<history>
<date date-type="received">
<day>12</day>
<month>02</month>
<year>2022</year>
</date>
<date date-type="accepted">
<day>28</day>
<month>03</month>
<year>2022</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#xa9; 2022 Janicka, Kanclerz, Wiatrowska and Budka.</copyright-statement>
<copyright-year>2022</copyright-year>
<copyright-holder>Janicka, Kanclerz, Wiatrowska and Budka</copyright-holder>
<license xlink:href="http://creativecommons.org/licenses/by/4.0/">
<p>This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.</p>
</license>
</permissions>
<abstract>
<p>River-lake systems in Central Europe represent the majority of surface water system forms. In these systems lakes play an important role in river water quality. Published reports on the quality of surface waters in Europe indicate progressive deterioration of their quality, resulting mainly from increasing eutrophication. This study analyzed the content of two biogenic elements&#x2014;nitrogen and phosphorus&#x2014;and their mineral forms in the G&#x142;uszynka river, representative for the river-lake systems of Central Europe. The research was conducted in the hydrological years 2016&#x2013;2018. The ecological status of the G&#x142;uszynka river, due to the &#x201c;poor&#x201d; status of both biological elements and physicochemical elements (content of phosphorus and nitrogen compounds), was classified as &#x201c;poor.&#x201d; In the period analyzed an increase in the content of nitrogen compounds was recorded in the hydrological year 2018. However, during the growing period a significant decrease in the content of total and nitrate nitrogen was observed, which was related to the activity of primary producers. For phosphorus compounds a slight increase of their content was observed during this period. This was associated with high tourist and recreational pressure on the analyzed system. Analyzing the spatial variability of biogenic compounds it was observed that along the course of the river the content of nitrite and nitrate nitrogen as well as total nitrogen increased at successive sampling points. An opposite trend of change along the river course was observed for phosphorus compounds (content of P-PO<sub>4</sub> and total phosphate decreased by 14 and 15.9%, respectively). Statistical analyses carried out highlighted the relationship between water quality and land use in the direct catchments of lakes included in the river-lake network. Arable land was associated with higher the content of orthophosphorus phosphate, grassland total nitrogen, nitrite and nitrate nitrogen, while urbanization was strongly associated with ammonium nitrogen.</p>
</abstract>
<kwd-group>
<kwd>river-lake system</kwd>
<kwd>nitrogen</kwd>
<kwd>phosphorus</kwd>
<kwd>water framework directive</kwd>
<kwd>eutrophication</kwd>
<kwd>river-lake interconnection</kwd>
<kwd>hydro-environmental</kwd>
</kwd-group>
<contract-num rid="cn001">Project No. 005/RID/2018/19</contract-num>
<contract-sponsor id="cn001">Uniwersytet Przyrodniczy w Poznaniu<named-content content-type="fundref-id">10.13039/501100005857</named-content>
</contract-sponsor>
</article-meta>
</front>
<body>
<sec id="s1">
<title>Introduction</title>
<p>Surface water resources around the world are under constant pressure. Rapidly growing populations leading to intensification of agricultural production and also human economic activities, increasing urbanization and climate change negatively affect water quality. Despite the implementation of the objectives of the Water Framework Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for community action in the field of water policy (OJ EU.L.00.327.1), the ecological status of surface waters in the European Union is still unsatisfactory. Detailed identification of pollution sources in catchment areas, their transfer routes to surface waters, and phenomena occurring in aquatic ecosystems are crucial for water protection. Failure to protect and improve water quality can lead to serious consequences in terms of the provisions of the Water Framework Directive as well as social consequences. Flowing waters as well as standing waters (natural and artificial reservoirs) that are polluted become useless to residents for both consumption and recreation. Therefore, in order to achieve at least their good ecological and chemical status, it is necessary to develop a water management plan and protect them from pollution such as surface runoff into watercourses. By consciously exploiting the relationships between catchment area processes, ecosystem capacity, resilience, and the ability to respond flexibly to threats can be increased.</p>
<p>The intensification of eutrophication processes in surface waters, especially in reservoirs, observed in recent years is related to many environmental factors. This process is caused by increased loads of phosphorus (P) and nitrogen (N) entering surface waters (<xref ref-type="bibr" rid="B64">Saunders and Kalff, 2001</xref>; <xref ref-type="bibr" rid="B20">Elser et al., 2007</xref>; <xref ref-type="bibr" rid="B12">Chislock et al., 2013</xref>; <xref ref-type="bibr" rid="B47">Li and Yao, 2015</xref>; <xref ref-type="bibr" rid="B69">Tan et al., 2017</xref>; <xref ref-type="bibr" rid="B45">Kuss et al., 2020</xref>; <xref ref-type="bibr" rid="B50">Matej-Lukowicz et al., 2020</xref>; <xref ref-type="bibr" rid="B70">Tao et al., 2021</xref>).</p>
<p>The main sources of phosphorus in surface waters are both raw and treated sewage, and stormwater entering the water body (<xref ref-type="bibr" rid="B53">Nausch et al., 2017</xref>; <xref ref-type="bibr" rid="B67">Stackpoole et al., 2019</xref>; <xref ref-type="bibr" rid="B56">Pietrzak et al., 2020</xref>). Because of its limited migratory capacity due to its bioaccumulation, sorption, and low solubility, phosphorous enters surface waters from surface runoff in smaller amounts than nitrogen ( <xref ref-type="bibr" rid="B35">Kanclerz et al., 2015</xref>; <xref ref-type="bibr" rid="B79">Wiatrowska and Komisarek, 2015</xref>). In areas intensively fertilized with phosphorus, this element may enter waters in larger quantities with surface runoff, but it migrates mostly in the form of adsorbed solid phase particles, and to a lesser extent in ionic form (<xref ref-type="bibr" rid="B28">Grabinska et al., 2004</xref>; <xref ref-type="bibr" rid="B58">Pokojska and Bednarek, 2021</xref>). This phenomenon applies in particular to sandy soils with low phosphorus retention capacity used for agricultural purposes. Due to the nature of lithogenic materials, such soils are common for the area of Poland (<xref ref-type="bibr" rid="B39">Kondracki, 2002</xref>).</p>
<p>Nitrogen compounds, on the other hand, enter surface waters mainly with surface runoff from agricultural areas and also with wastewater, or as precipitation (<xref ref-type="bibr" rid="B19">Dojlido 1995</xref>; <xref ref-type="bibr" rid="B1">Allan 2004</xref>; <xref ref-type="bibr" rid="B49">Lossow et al., 2006</xref>; <xref ref-type="bibr" rid="B10">Causse et al., 2015</xref>; <xref ref-type="bibr" rid="B8">Burzy&#x144;ska 2019</xref>; <xref ref-type="bibr" rid="B45">Kuss et al., 2020</xref>). Between 1961 and 2000, there was a significant increase in global nitrate fertiliser use (by about 600%), which had a major impact on surface water quality (<xref ref-type="bibr" rid="B62">Revenga et al., 2000</xref>).</p>
<p>According to the European Environment Agency, surface water pollution in the European Union is mainly related to agricultural pressures, and due to significant spatial differences related to climate, soil type and chemistry, geological conditions, topography and diverse agricultural activities, the negative impact of nutrients on surface waters varies across the EU (<xref ref-type="bibr" rid="B75">Vagstad et al., 2004</xref>; <xref ref-type="bibr" rid="B40">Kristenen, 2012</xref>). Recent research by the European Environment Agency (EEA) shows that measures to reduce emissions of nitrogen and phosphorus compounds have led to improvements in surface water quality. According to the Water Framework Directive, European Union Member States should aim to achieve at least good water status, but only 44% of surface waters in Europe achieve good or very good ecological status (<xref ref-type="bibr" rid="B5">Bruyninckx, 2020</xref>). According to the EEA report, Belgium, Hungary and Denmark had the lowest surface water quality compared to other European countries. Poland ranks slightly better in this classification, as nearly 50% of the surface waters studied were classified as surface waters with good or very good ecological status (<xref ref-type="bibr" rid="B41">Kristensen et al., 2018</xref>).</p>
<p>One of the main parameters affecting surface water quality is the way in which the catchment area is developed and used (<xref ref-type="bibr" rid="B83">Ye et al., 2013</xref>; <xref ref-type="bibr" rid="B59">Potasznik and Szymczyk, 2015</xref>; <xref ref-type="bibr" rid="B82">Yang et al., 2016</xref>; <xref ref-type="bibr" rid="B42">Kuriata-Potasznik et al., 2018</xref>; <xref ref-type="bibr" rid="B18">Djodjic et al., 2021</xref>). Reservoirs and rivers located in lowland areas, whose catchment areas are intensively used for agriculture, are particularly exposed to the eutrophication process. At the same time, these areas are dominated by river-lake systems (<xref ref-type="bibr" rid="B64">Saunders and Kalff, 2001</xref>; <xref ref-type="bibr" rid="B25">Foley et al., 2005</xref>; <xref ref-type="bibr" rid="B17">Dabrowska, 2008</xref>; <xref ref-type="bibr" rid="B81">Woli et al., 2008</xref>; <xref ref-type="bibr" rid="B77">Varanka and Luoto, 2012</xref>; <xref ref-type="bibr" rid="B3">Bajkiewicz-Grabowska et al., 2020</xref>). According to <xref ref-type="bibr" rid="B44">Kuriata-Potasznik (2018)</xref>, in these systems, rivers act as transporters of nutrients while lakes serve as temporary retention sites. The processes of nutrient deposition in the bottom sediments of lakes depend on the physicochemical conditions in the water body. At the same time, the assimilation of nutrients by primary producers occurs in lakes during the growing period, which consequently reduces the content of these elements in surface waters (<xref ref-type="bibr" rid="B64">Saunders and Kalff, 2001</xref>; <xref ref-type="bibr" rid="B68">Sun et al., 2018</xref>; <xref ref-type="bibr" rid="B74">Uuemaa et al., 2018</xref>). Depending on the processes occurring in lakes, different trends of water quality changes were observed in the rivers below them. Thus, in river-lake systems, both improvement and deterioration of water quality parameters are observed depending on the element considered as well as changes in the activity of primary producers. A large role in shaping the chemistry of river waters is played by bottom sediments, which on the one hand can accumulate nutrients, temporarily excluding them from the biological cycle, or release them into the water (<xref ref-type="bibr" rid="B30">Hillbricht-Ilkowska, 1999</xref>; <xref ref-type="bibr" rid="B27">Gli&#x144;ska-Lewczuk, 2006</xref>; <xref ref-type="bibr" rid="B65">Sobczy&#x144;ska-W&#xf3;jcik and Rafa&#x142;owska, 2011</xref>; <xref ref-type="bibr" rid="B43">Kuriata-Potasznik et al., 2020</xref>). Previous work dealing with water quality in river-lake systems has focused primarily on analyzing the total content of various elements, mainly biogenic. Unfortunately, there are no data on the behavior of individual chemical forms of biogens, especially nitrogen, which determine their bioavailability and thus the quality of aquatic ecosystems.</p>
<p>The study analyzed the temporal and spatial variability of phosphorus and nitrogen and their mineral forms in the waters of the river-lake system of the G&#x142;uszynka river. The results of the study were related to the land use of the catchment area, in order to make an attempt to indicate the main causes of water quality deterioration in the analyzed catchment area. For this purpose, the following hypotheses were formulated: 1) The quality of surface waters depends primarily on the way the catchment is used. The study assumes that agricultural and urbanized areas with incomplete sewage management will contribute to an increased content of nutrients, especially nitrogen and phosphorus, as opposed to forest areas, where the content of these elements in water should decrease. 2) Taking into account the biogeochemistry of nitrogen, it was assumed that both in the case of the content of total nitrogen and mineral forms of nitrogen, an increase in their content would be observed along the course of the river. On the other hand, in the case of phosphorus, which is easily precipitated, its concentration will decrease along with the flow through reservoirs with a longer water residence times (longer than 1&#xa0;year). 3) The dynamics of changes in nitrogen content and its forms will be influenced by the activity of primary producers. For phosphorus, due to the possible supply from bottom sediments, such an effect will not be observed. To test these hypotheses, we analyzed data collected from 7 sampling points located along the G&#x142;uszynka river course for the period of hydrological years 2016&#x2013;2018 (<xref ref-type="fig" rid="F1">Figure 1</xref>).</p>
<fig id="F1" position="float">
<label>FIGURE 1</label>
<caption>
<p>Study site location.</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g001.tif"/>
</fig>
</sec>
<sec sec-type="materials|methods" id="s2">
<title>Methods and Materials</title>
<sec id="s2-1">
<title>Study Area</title>
<p>The catchment area of the G&#x142;uszynka river is 134.72&#xa0;km<sup>2</sup> and it is situated in central-western Poland. According to the physico-geographical division of Poland it is located in the south of the Baltic Lakelands (<xref ref-type="bibr" rid="B39">Kondracki, 2002</xref>). The study area is located within the range of the Weichselian glaciation.</p>
<p>According to Corine Land Cover 2018, 60% of the catchment area is dominated by agricultural land. The largest part of the area is non-irrigated arable land coded 211. Anthropogenic land constitutes 10.41&#xa0;km<sup>2</sup> (7.87% of the catchment area) with a predominance of discontinuous urban fabric (code 112). In turn, forests and semi-natural ecosystems constitute an area of 32.56&#xa0;km<sup>2</sup> (24.63%) (<xref ref-type="fig" rid="F2">Figure 2</xref>). The attractive location and natural values of the K&#xf3;rnik-Zaniemyska Gutter make the lakes particularly interesting for tourists, which may be an additional burden for the catchment area (<xref ref-type="bibr" rid="B63">Rosi&#x144;ska and Go&#x142;dyn 2018</xref>).</p>
<fig id="F2" position="float">
<label>FIGURE 2</label>
<caption>
<p>Structure of land use of the G&#x142;uszynka river catchment area (source: <xref ref-type="bibr" rid="B14">CLC 2018</xref>).</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g002.tif"/>
</fig>
<p>The 24.4&#xa0;km long river-lake system of the G&#x142;uszynka river consists of eight lakes in the K&#xf3;rnik-Zaniemy&#x15b;l Gutter connected by short sections of river, where the ratio of the length of the river sections to the total length of the river sections flowing through the lakes is 0.62. The source of the G&#x142;uszynka river is considered to be Lake Raczy&#x144;skie. The river then flows through the following lakes: &#x141;&#x119;kno, Jeziory Ma&#x142;e, Jeziory Wielkie, Bni&#x144;skie, K&#xf3;rnickie, Skrzynki Du&#x17c;e and Skrzynki Ma&#x142;e (<xref ref-type="fig" rid="F1">Figure 1</xref>). The largest lake of this river-lake system is Lake Bni&#x144;skie (0.225&#xa0;km<sup>2</sup>).</p>
<p>Taking into account the land use structure of the immediate catchment areas of the lakes of the studied system, two groups of catchments were distinguished in the study: agricultural (with the percentage of agricultural land from 58.8 to 81.7%) and forest-agricultural (with the share of forests and semi-natural ecosystems from 35.2 to 71.4%) (<xref ref-type="table" rid="T1">Table 1</xref>). This division of the immediate catchments was performed using the agglomeration method in the Statistica 13.3 program. (TIBCO Software Inc., United States).</p>
<table-wrap id="T1" position="float">
<label>TABLE 1</label>
<caption>
<p>Basic characteristics of lakes of the K&#xf3;rnik-Zaniemyska Gutter (source: <xref ref-type="bibr" rid="B13">Choi&#x144;ski 2006</xref>, own research).</p>
</caption>
<table>
<thead valign="top">
<tr>
<th rowspan="2" align="left">No.</th>
<th rowspan="2" align="center">Lake</th>
<th rowspan="2" align="center">Lake area [km<sup>2</sup>]</th>
<th rowspan="2" align="center">Maximum depth [m]</th>
<th rowspan="2" align="center">Average depth [m]</th>
<th colspan="2" align="center">Percentage of land</th>
<th rowspan="2" align="center">Dominant type of use</th>
</tr>
<tr>
<th align="center">agricultural</th>
<th align="center">forestry</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td align="left">1</td>
<td align="left">Raczy&#x144;skie</td>
<td align="char" char=".">0.908</td>
<td align="char" char=".">5.8</td>
<td align="char" char=".">2.8</td>
<td align="char" char=".">58.8</td>
<td align="char" char=".">26.2</td>
<td align="left">agricultural</td>
</tr>
<tr>
<td align="left">2</td>
<td align="left">&#x141;&#x119;kno</td>
<td align="char" char=".">0.273</td>
<td align="char" char=".">5.0</td>
<td align="char" char=".">2.2</td>
<td align="char" char=".">21.6</td>
<td align="char" char=".">71.4</td>
<td align="left">forestry-agricultural</td>
</tr>
<tr>
<td align="left">3</td>
<td align="left">Jeziory Ma&#x142;e</td>
<td align="char" char=".">0.513</td>
<td align="char" char=".">16.3</td>
<td align="char" char=".">5.9</td>
<td align="char" char=".">21.3</td>
<td align="char" char=".">35.2</td>
<td align="left">forestry-agricultural</td>
</tr>
<tr>
<td align="left">4</td>
<td align="left">Jeziory Wielkie</td>
<td align="char" char=".">0.688</td>
<td align="char" char=".">5.4</td>
<td align="char" char=".">3.0</td>
<td align="char" char=".">65.9</td>
<td align="char" char=".">25.9</td>
<td align="left">agricultural</td>
</tr>
<tr>
<td align="left">5</td>
<td align="left">Bni&#x144;skie</td>
<td align="char" char=".">2.333</td>
<td align="char" char=".">8.5</td>
<td align="char" char=".">4.2</td>
<td align="char" char=".">75.2</td>
<td align="char" char=".">9.3</td>
<td align="left">agricultural</td>
</tr>
<tr>
<td align="left">6</td>
<td align="left">K&#xf3;rnickie</td>
<td align="char" char=".">0.760</td>
<td align="char" char=".">6.0</td>
<td align="char" char=".">2.6</td>
<td align="char" char=".">81.7</td>
<td align="char" char=".">8.4</td>
<td align="left">agricultural</td>
</tr>
<tr>
<td align="left">7</td>
<td align="left">Skrzynki Du&#x17c;e</td>
<td align="char" char=".">0.723</td>
<td align="char" char=".">6.5</td>
<td align="char" char=".">3.4</td>
<td align="char" char=".">81.1</td>
<td align="char" char=".">9.6</td>
<td align="left">agricultural</td>
</tr>
<tr>
<td align="left">8</td>
<td align="left">Skrzynki Ma&#x142;e</td>
<td align="char" char=".">0.163</td>
<td align="char" char=".">8.0</td>
<td align="char" char=".">3.9</td>
<td align="char" char=".">25.7</td>
<td align="char" char=".">66.3</td>
<td align="left">forestry-agricultural</td>
</tr>
</tbody>
</table>
</table-wrap>
<p>The catchment area is mainly covered with Luvisols. The parent materials of these soils are glacial till and loamy sand. The analysed catchment area consists mostly of coarse-textured soils. It is dominated by fine loamy sand (<xref ref-type="sec" rid="s11">Supplementary Table S1</xref>). These are easily permeable formations with low retention capacity, and in the case of intensive fertilization of these soils, there is a real risk of rapid transport of nutrients to surface and groundwaters.</p>
</sec>
<sec id="s2-2">
<title>Cartographic Works</title>
<p>The cartographic works involved an analysis of the structure of the catchment area according to Corine Land Cover 2018 and a morphometric analysis of the lakes of the K&#xf3;rnik-Zaniemyska Gutter. In terms of the land use structure of the immediate catchment area of the lakes, two groups of catchment areas were distinguished: agricultural (agricultural areas from 58.8 to 81.7%) and forest-agricultural (forest areas from 35.2 to 71.4%). All spatial analyses were performed using ArcMap 10.7.1.</p>
<p>The meteorological data were provided by the Institute of Meteorology and Water Management&#x2014;National Research Institute, for the period from 1990 to 2019. The classification of precipitation condition of individual years studied was performed according to the methodology of <xref ref-type="bibr" rid="B34">Kaczorowska (1962)</xref>. In this classification, the precipitation was calculated on the basis of the percentage of precipitation in a given year over the multi-year average (at least 30 years) (<xref ref-type="bibr" rid="B80">WMO 2009</xref>). The thermal condition classification was performed according to the method developed by <xref ref-type="bibr" rid="B48">Lorenc (2000)</xref>. Characteristics such as average temperature, average value for the multi-year period and standard deviation for the multi-year period were used in the thermal classification.</p>
<p>The assessment of the ecological status of surface waters was made on the basis of the Regulation of the Minister of Infrastructure of 25<sup>th</sup> June, 2021 (<xref ref-type="bibr" rid="B33">Journal of Laws 2021, item 1475, 2021</xref>) on the basis of the evaluation of biological elements obtained from the Inspectorate of Environmental Protection (<xref ref-type="bibr" rid="B26">GIO&#x15a;, 2018</xref>) and physicochemical elements.</p>
</sec>
<sec id="s2-3">
<title>Field Works</title>
<p>The samples of surface water for the laboratory analyses were collected from 7 sampling points (sp) located on the G&#x142;uszynka river and they were marked with the alphanumeric code (G1-G7) (<xref ref-type="fig" rid="F1">Figure 1</xref>), at a frequency of once per month during hydrological years in the period 2016 to 2018. The water samples were collected in 1&#xa0;L polyethylene bottles which were transported afterwards at the temperature of 4&#xb0;C and analyzed in the laboratory within 48&#xa0;h of their collection.</p>
<p>In the profiles located on the river, measurements of the water flow velocity were carried out using a Valeport hydrometric mill, and the water flow intensity in the river was calculated using the Harlacher calculation method (<xref ref-type="bibr" rid="B9">Byczkowski, 1996</xref>). The water exchange in lakes was determined on the basis of the capacity of the lake basin and the average river water flows in the sections between the lakes (above and below the lake).</p>
<p>Taking into account the predominantly agricultural nature of the catchment area, the abundance of available phosphorus in the soils was also analyzed. For this purpose, 18 composite soil samples were collected from the lakeshore of the studied river-lake system (<xref ref-type="fig" rid="F2">Figure 2</xref>). The samples were collected based on a cross-shaped plan with an arm length of 1 meter, in duplicate from the surface horizon (0&#x2013;20&#xa0;cm).</p>
</sec>
<sec id="s2-4">
<title>Laboratory Work</title>
<p>The following parameters were determined in the collected samples of surface water: total nitrogen, ammonium nitrogen, nitrite nitrogen, nitrate nitrogen, total phosphorus and orthophosphate phosphorous (V). The measurements were done in accordance with the current standard. The analyses were performed in duplicate and the data were presented as averaged values. The content of total nitrogen was determined by Koroleff&#x2019;s method according to the standard BS EN ISO 11905-1:1998 (Water quality. Determination of nitrogen) with measurement uncertainty 0.15&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup>. Mineral forms of nitrogen were determined spectrophotometrically using <xref ref-type="bibr" rid="B23">EPA method 354.1</xref> (Nitrite by Spectrophotometry) with measurement uncertainty 0.02&#xa0;mg&#xa0;N-NO<sub>3</sub>&#xa0;dm<sup>&#x2212;3</sup> and with measurement uncertainty 0.0083&#xa0;mg&#xa0;N-NO<sub>2</sub>&#xa0;dm<sup>&#x2212;3</sup>, but <xref ref-type="bibr" rid="B22">EPA method 350.1</xref> (Determination of ammonia nitrogen by semi-automated colorimetry) for N-NH<sub>4</sub> with measurement uncertainty 0.01&#xa0;mg&#xa0;N-NH<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup>.</p>
<p>The concentration of orthophosphate phosphorous (V). and total phosphorus was determined according to the method <xref ref-type="bibr" rid="B21">EN ISO 6878, (2004)</xref>. The content was measured using ammonium molybdate and ascorbic acid at 712&#xa0;nm on a JENWAY instrument (7315 Spectrophotometer). However, total phosphorus content was determined after mineralization with ammonium persulfate. Measurement uncertainty for orthophosphate phosphorous (V) and for total phosphorous was 0.044&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>.</p>
<p>The soil texture was determined by Casagrande&#x2019;s areometric method, modified by Pr&#xf3;szy&#x144;ski according to <xref ref-type="bibr" rid="B57">PN-R-040032 standard (1998)</xref>. The fine particles (smaller than &#x2205;&#x3c; 0.05&#xa0;mm) were determined with the sedimentation method and in the case of the larger ones (0.05&#x2013;2.00&#xa0;mm) the sieve method was applied. The soil texture samples were classified according to the standards of the United States Department of Agriculture. The content of available phosphorus was determined using the Egner method (<xref ref-type="bibr" rid="B51">Mocek et al., 2006</xref>). The analyses were performed in duplicate and the results are presented as averaged values. For this study, an internal reference sample was used to check the accuracy of the performed analyses.</p>
<p>Other parameters were also determined during field and laboratory work: dissolved oxygen, temperature, EC, pH, BOD<sub>5</sub>, SO<sub>4</sub>
<sup>2&#x2212;</sup>, Cl, H-CO<sub>3</sub>
<sup>&#x2212;</sup> and metal cations Na<sup>&#x2b;</sup>, K<sup>&#x2b;</sup>, Mg<sup>2&#x2b;</sup>, Ca<sup>2&#x2b;</sup> (data not shown).</p>
</sec>
<sec id="s2-5">
<title>Statistical Analyses</title>
<p>Data in the study are presented as average values, in the case of water analysis results <italic>n</italic> &#x3d; 9 and for soil samples <italic>n</italic> &#x3d; 2. Both the spatial and temporal variability of selected parameters of surface water quality were analyzed. Due to the clear seasonal variability of parameters in the analysis of temporal variability, the sampling dates were divided into two groups: the growing period and the non-vegetative period. Months were separated into particular periods on the basis of the analysis of average daily air temperatures for individual months. The threshold temperature &#x2265; 5&#xb0;C was adopted for a growing period. (<xref ref-type="bibr" rid="B72">Tomczyk and Szyga-Pluta, 2016</xref>).</p>
<p>In order to identify environmental factors influencing the content of nitrogen and phosphorus and their mineral forms in surface waters, principal component analysis (PCA) was used. This statistical analysis was performed using the Statistica 13.3 program (TIBCO Software Inc., United States). The PCA results were presented as biplots (<xref ref-type="bibr" rid="B52">Morrison, 1990</xref>; <xref ref-type="bibr" rid="B24">Falniowski, 2003</xref>). Parametric statistical change point analysis was used to determine the critical point of change in the content of the analysed parameters of surface water quality along the river course (<xref ref-type="bibr" rid="B15">Cobb, 1978</xref>; <xref ref-type="bibr" rid="B36">Killick and Eckley, 2014</xref>). This analysis was performed using the R program (R Development Core Team 2019).</p>
</sec>
</sec>
<sec sec-type="results" id="s3">
<title>Results</title>
<sec id="s3-1">
<title>Characteristics of the Catchment Area</title>
<p>The catchment area of the G&#x142;uszynka river is characterized by the lowest annual rainfall in Poland. The average annual rainfall recorded in the years 1989&#x2013;2018 was 571&#xa0;mm, and the average annual air temperature in these years was 9.3&#xb0;C. The hydrological years 2016&#x2013;2018 in which the research was conducted were classified on the basis of precipitation as wet (2016), very wet (2017) and normal (2018), in which the sums of annual rainfall accounted for 125.99, 126.83 and 106.14% of the average multi-year precipitation, respectively (<xref ref-type="sec" rid="s11">Supplementary Figures S1, S2</xref>). During the research period, the occurrence of torrential rains was recorded on 14<sup>th</sup> July 2016 (64.3&#xa0;mm), in July 2017 (150.6&#xa0;mm) and on 2<sup>nd</sup> June 2018 (99.3&#xa0;mm), which resulted in an increase in the water flow in the river. Thermally, the hydrological years 2016 and 2018 were classified as warm, while 2017 was classified as normal.</p>
<p>The average of the mean annual flows of the G&#x142;uszynka river in the G7 water gauge profile in 2016&#x2013;2018 was (SSQ) 0.39&#xa0;m<sup>3</sup>&#xa0;s<sup>&#x2212;1</sup>, and the extreme flows ranged from the lowest annual low flow (NNQ), 0.047&#xa0;m<sup>3</sup>&#xa0;s<sup>&#x2212;1</sup> (12.07.2016), noted for G6, located between the lakes Skrzynki Du&#x17c;e and Skrzynki Ma&#x142;e to the highest annual high flow (WWQ), 2.18&#xa0;m<sup>3</sup>&#xa0;s<sup>&#x2212;1</sup> (02.02.2018). The lowest average flow in this profile was recorded in 2016 (NSQ &#x3d; 0.23&#xa0;m<sup>3</sup>&#xa0;s<sup>&#x2212;1</sup>) and the highest in 2018 (WSQ &#x3d; 0.55&#xa0;m<sup>3</sup>&#xa0;s<sup>&#x2212;1</sup>). The average annual unit outflow in 2016&#x2013;2018 was 2.89&#xa0;dm<sup>3</sup>&#xa0;s<sup>&#x2013; 1</sup>&#xa0;km<sup>&#x2013;2</sup>, and the impact on the river outflow ratio was 0.13. The lakes &#x141;&#x119;kno and Jeziory Ma&#x142;e are connected by a concrete culvert, so no sampling point was designated between these lakes.</p>
<p>The water residence times in the lakes of the K&#xf3;rnik-Zaniemyska Gutter was diverse : Raczy&#x144;skie Lake 14&#xa0;months, Lake &#x141;&#x119;kno 78&#xa0;months, Lake Jeziory Ma&#x142;e 18&#xa0;months, Lake Jeziory Wielkie 37&#xa0;months, Lake Bni&#x144;skie 7&#xa0;months, Lake K&#xf3;rnickie 65&#xa0;months, Lake Skrzynki Du&#x17c;e 9&#xa0;months and Lake Skrzynki Ma&#x142;e 16&#xa0;months.</p>
</sec>
<sec id="s3-2">
<title>Spatial Variability of the Content of Nitrogen and Phosphorus and Their Forms</title>
<p>The quality of surface waters, in accordance with the provisions of the Water Directive, is assessed on the basis of biological elements supported by physicochemical elements. This article focuses more on the temporal and spatial variability of nutrient content in the G&#x142;uszynka river, observed in the hydrological years 2016&#x2013;2018. Taking into account the fact that the availability of nutrients significantly influences the growth of primary producers, the study tried to determine how the use of the catchment area and the rate of water change in water reservoirs affect their content in waters. However, the final assessment of the G&#x142;uszynka river waters presented in the paper takes into account both factors required by the Water Directive.</p>
<p>The content of total nitrogen in the G&#x142;uszynka river during the hydrological years 2016&#x2013;2018, ranged from 0.87&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup>&#x2013;9.32&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup>. The highest mean content of total nitrogen was observed at sp G6 (3.87&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup>) and the lowest at sp G1 (2.31&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup>) (<xref ref-type="table" rid="T2">Table 2</xref>). For mineral forms, a slightly different pattern of changes in the average content in individual sampling points was observed. Only the form with the highest oxidation state showed similar changes with the course of the river. The highest mean content of nitrate nitrogen was observed at point G5 (2.43&#xa0;mg&#xa0;N-NO<sub>3</sub>&#xa0;dm<sup>&#x2212;3</sup>), and the lowest at point G1 (1.21&#xa0;mg&#xa0;N-NO<sub>3</sub>&#xa0;dm<sup>&#x2212;3</sup>). In the case of nitrite nitrogen, the values of this nitrogen speciation ranged from 0.06 to 0.44&#xa0;mg&#xa0;N-NO<sub>2</sub>&#xa0;dm<sup>&#x2212;3</sup>. The lowest mean content of this form of nitrogen was recorded at point G1 (0.08&#xa0;mg&#xa0;N-NO<sub>2</sub>&#xa0;dm<sup>&#x2212;3</sup>), below Lake Raczy&#x144;skie, while the highest mean content of nitrite nitrogen was observed below Lake Skrzynki Du&#x17c;e (G6), 0.14&#xa0;mg&#xa0;N-NO<sub>2</sub>&#xa0;dm<sup>&#x2212;3</sup>. The highest mean content of ammonium nitrogen was recorded at G2 (0.130&#xa0;mg&#xa0;N-NH<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup>), and the lowest at G4 (0.102&#xa0;mg&#xa0;N-NH<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup>) (<xref ref-type="fig" rid="F3">Figures 3A&#x2013;D</xref>). With nitrite and nitrate nitrogen as well as total nitrogen, a tendency of an increase in the content of these pools of nitrogen was observed along with the course of the river. The average content of nitrite nitrogen increased by 50% (G1&#x2014;0.08 to G7&#x2014;0.12&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>), total nitrogen by 67% (G1&#x2014;2.31 to G7&#x2014;3.86&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>) and nitrate nitrogen by 100% (G1 &#x2013;1.21 to G7&#x2014;2.42&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>). In the case of total nitrogen, nitrite and nitrate forms, a significant increase in the value from sp G4 below Lake Bni&#x144;skie was observed (<xref ref-type="fig" rid="F3">Figures 3A&#x2013;C</xref>). The increase in the mean content of these parameters from sp G1 to G4 was 44.55, 25.85 and 68.12% for total nitrogen, nitrite and nitrate nitrogen, respectively. The parametric statistical change point analysis performed confirmed that a significant increase in the content of nitrate nitrogen and total nitrogen occurred between G4 and G5 sites, and for nitrite nitrogen between G3 and G4 sites (<xref ref-type="fig" rid="F4">Figures 4A&#x2013;C</xref>). The above-mentioned change points were assigned on the basis of statistically significant changes in the values of these parameters.</p>
<table-wrap id="T2" position="float">
<label>TABLE 2</label>
<caption>
<p>Water quality indicators of the G&#x142;uszynka river during the hydrological years 2016&#x2013;2018, broken down into growing and non-vegetative period.</p>
</caption>
<table>
<thead valign="top">
<tr>
<th rowspan="2" align="left">Index</th>
<th rowspan="2" align="left"/>
<th colspan="3" align="center">Hydrological year</th>
<th colspan="3" align="center">Growing period</th>
<th colspan="3" align="center">Non-vegetative period</th>
</tr>
<tr>
<th align="center">2016</th>
<th align="center">2017</th>
<th align="center">2018</th>
<th align="center">2016</th>
<th align="center">2017</th>
<th align="center">2018</th>
<th align="center">2016</th>
<th align="center">2017</th>
<th align="center">2018</th>
</tr>
</thead>
<tbody valign="top">
<tr>
<td rowspan="4" align="left">N [mg&#x2219;dm<sup>&#x2212;3</sup>]</td>
<td align="left">Range</td>
<td align="char" char=".">1.54&#x2013;4.59</td>
<td align="char" char=".">0.87&#x2013;8.61</td>
<td align="char" char=".">1.56&#x2013;9.32</td>
<td align="char" char=".">1.54&#x2013;4.53</td>
<td align="char" char=".">0.87&#x2013;5.83</td>
<td align="char" char=".">1.56&#x2013;6.16</td>
<td align="char" char=".">2.25&#x2013;4.59</td>
<td align="char" char=".">1.50&#x2013;8.61</td>
<td align="char" char=".">2.84&#x2013;9.32</td>
</tr>
<tr>
<td align="left">Average</td>
<td align="char" char=".">2.59</td>
<td align="char" char=".">3.26</td>
<td align="char" char=".">3.76</td>
<td align="char" char=".">2.35</td>
<td align="char" char=".">2.06</td>
<td align="char" char=".">3.17</td>
<td align="char" char=".">3.56</td>
<td align="char" char=".">4.76</td>
<td align="char" char=".">6.12</td>
</tr>
<tr>
<td align="left">SD</td>
<td align="char" char=".">0.82</td>
<td align="char" char=".">2.16</td>
<td align="char" char=".">1.91</td>
<td align="char" char=".">0.04</td>
<td align="char" char=".">0.05</td>
<td align="char" char=".">0.01</td>
<td align="char" char=".">0.04</td>
<td align="char" char=".">0.09</td>
<td align="char" char=".">0.05</td>
</tr>
<tr>
<td align="left">V</td>
<td align="char" char=".">31.71</td>
<td align="char" char=".">66.42</td>
<td align="char" char=".">50.69</td>
<td align="char" char=".">25.74</td>
<td align="char" char=".">59.54</td>
<td align="char" char=".">36.84</td>
<td align="char" char=".">25.23</td>
<td align="char" char=".">45.35</td>
<td align="char" char=".">51.51</td>
</tr>
<tr>
<td rowspan="4" align="left">N-NO<sub>3</sub> [mg&#x2219;dm<sup>&#x2212;3</sup>]</td>
<td align="left">Range</td>
<td align="char" char=".">0.56&#x2013;3.00</td>
<td align="char" char=".">0.07&#x2013;6.35</td>
<td align="char" char=".">0.55&#x2013;6.95</td>
<td align="char" char=".">0.56&#x2013;3.00</td>
<td align="char" char=".">0.07&#x2013;3.98</td>
<td align="char" char=".">0.55&#x2013;4.30</td>
<td align="char" char=".">1.20&#x2013;3.00</td>
<td align="char" char=".">0.40&#x2013;6.35</td>
<td align="char" char=".">1.40&#x2013;6.95</td>
</tr>
<tr>
<td align="left">Average</td>
<td align="char" char=".">1.40</td>
<td align="char" char=".">1.93</td>
<td align="char" char=".">2.39</td>
<td align="char" char=".">1.20</td>
<td align="char" char=".">0.99</td>
<td align="char" char=".">1.93</td>
<td align="char" char=".">2.21</td>
<td align="char" char=".">3.11</td>
<td align="char" char=".">4.24</td>
</tr>
<tr>
<td align="left">SD</td>
<td align="char" char=".">0.67</td>
<td align="char" char=".">1.73</td>
<td align="char" char=".">1.54</td>
<td align="char" char=".">0.50</td>
<td align="char" char=".">0.95</td>
<td align="char" char=".">0.95</td>
<td align="char" char=".">0.69</td>
<td align="char" char=".">1.76</td>
<td align="char" char=".">2.55</td>
</tr>
<tr>
<td align="left">V</td>
<td align="char" char=".">48.09</td>
<td align="char" char=".">89.41</td>
<td align="char" char=".">64.35</td>
<td align="char" char=".">41.73</td>
<td align="char" char=".">96.49</td>
<td align="char" char=".">49.57</td>
<td align="char" char=".">31.25</td>
<td align="char" char=".">56.66</td>
<td align="char" char=".">60.05</td>
</tr>
<tr>
<td rowspan="4" align="left">N-NO<sub>2</sub> [mg&#x2219;dm<sup>&#x2212;3</sup>]</td>
<td align="left">Range</td>
<td align="char" char=".">0.06&#x2013;0.18</td>
<td align="char" char=".">0.05&#x2013;0.44</td>
<td align="char" char=".">0.06&#x2013;0.26</td>
<td align="char" char=".">0.06&#x2013;0.18</td>
<td align="char" char=".">0.05&#x2013;0.26</td>
<td align="char" char=".">0.06&#x2013;0.1</td>
<td align="char" char=".">0.08&#x2013;0.18</td>
<td align="char" char=".">0.06&#x2013;0.44</td>
<td align="char" char=".">0.07&#x2013;0.26</td>
</tr>
<tr>
<td align="left">Average</td>
<td align="char" char=".">0.10</td>
<td align="char" char=".">0.12</td>
<td align="char" char=".">0.08</td>
<td align="char" char=".">0.09</td>
<td align="char" char=".">0.10</td>
<td align="char" char=".">0.07</td>
<td align="char" char=".">0.13</td>
<td align="char" char=".">0.14</td>
<td align="char" char=".">0.13</td>
</tr>
<tr>
<td align="left">SD</td>
<td align="char" char=".">0.04</td>
<td align="char" char=".">0.07</td>
<td align="char" char=".">0.04</td>
<td align="char" char=".">0.04</td>
<td align="char" char=".">0.05</td>
<td align="char" char=".">0.01</td>
<td align="char" char=".">0.04</td>
<td align="char" char=".">0.09</td>
<td align="char" char=".">0.05</td>
</tr>
<tr>
<td align="left">V</td>
<td align="char" char=".">41.18</td>
<td align="char" char=".">61.75</td>
<td align="char" char=".">49.55</td>
<td align="char" char=".">41.10</td>
<td align="char" char=".">48.17</td>
<td align="char" char=".">19.93</td>
<td align="char" char=".">30.52</td>
<td align="char" char=".">66.64</td>
<td align="char" char=".">41.91</td>
</tr>
<tr>
<td rowspan="4" align="left">N-NH<sub>4</sub> [mg&#x2219;dm<sup>&#x2212;3</sup>]</td>
<td align="left">Range</td>
<td align="char" char=".">0.06&#x2013;0.41</td>
<td align="char" char=".">0.06&#x2013;0.38</td>
<td align="char" char=".">0.03&#x2013;0.28</td>
<td align="char" char=".">0.06&#x2013;0.41</td>
<td align="char" char=".">0.06&#x2013;0.20</td>
<td align="char" char=".">0.06&#x2013;0.27</td>
<td align="char" char=".">0.06&#x2013;0.08</td>
<td align="char" char=".">0.06&#x2013;0.38</td>
<td align="char" char=".">0.03&#x2013;0.28</td>
</tr>
<tr>
<td align="left">Average</td>
<td align="char" char=".">0.12</td>
<td align="char" char=".">0.11</td>
<td align="char" char=".">0.11</td>
<td align="char" char=".">0.13</td>
<td align="char" char=".">0.09</td>
<td align="char" char=".">0.10</td>
<td align="char" char=".">0.07</td>
<td align="char" char=".">0.14</td>
<td align="char" char=".">0.14</td>
</tr>
<tr>
<td align="left">SD</td>
<td align="char" char=".">0.09</td>
<td align="char" char=".">0.07</td>
<td align="char" char=".">0.06</td>
<td align="char" char=".">0.09</td>
<td align="char" char=".">0.03</td>
<td align="char" char=".">0.05</td>
<td align="char" char=".">0.01</td>
<td align="char" char=".">0.09</td>
<td align="char" char=".">0.07</td>
</tr>
<tr>
<td align="left">V</td>
<td align="char" char=".">70.95</td>
<td align="char" char=".">58.68</td>
<td align="char" char=".">61.22</td>
<td align="char" char=".">68.09</td>
<td align="char" char=".">35.90</td>
<td align="char" char=".">56.45</td>
<td align="char" char=".">10.08</td>
<td align="char" char=".">61.67</td>
<td align="char" char=".">48.55</td>
</tr>
<tr>
<td rowspan="4" align="left">P [mg&#x2219;dm<sup>&#x2212;3</sup>]</td>
<td align="left">Range</td>
<td align="char" char=".">0.11&#x2013;0.55</td>
<td align="char" char=".">0.08&#x2013;1.76</td>
<td align="char" char=".">0.11&#x2013;0.55</td>
<td align="char" char=".">0.11&#x2013;0.55</td>
<td align="char" char=".">0.08&#x2013;1.76</td>
<td align="char" char=".">0.11&#x2013;0.55</td>
<td align="char" char=".">0.38&#x2013;0.53</td>
<td align="char" char=".">0.08&#x2013;0.58</td>
<td align="char" char=".">0.38&#x2013;0.53</td>
</tr>
<tr>
<td align="left">Average</td>
<td align="char" char=".">0.36</td>
<td align="char" char=".">0.40</td>
<td align="char" char=".">0.36</td>
<td align="char" char=".">0.34</td>
<td align="char" char=".">0.45</td>
<td align="char" char=".">0.34</td>
<td align="char" char=".">0.45</td>
<td align="char" char=".">0.33</td>
<td align="char" char=".">0.45</td>
</tr>
<tr>
<td align="left">SD</td>
<td align="char" char=".">0.11</td>
<td align="char" char=".">0.27</td>
<td align="char" char=".">0.11</td>
<td align="char" char=".">0.33</td>
<td align="char" char=".">0.45</td>
<td align="char" char=".">0.33</td>
<td align="char" char=".">0.06</td>
<td align="char" char=".">0.15</td>
<td align="char" char=".">0.48</td>
</tr>
<tr>
<td align="left">V</td>
<td align="char" char=".">32.02</td>
<td align="char" char=".">67.27</td>
<td align="char" char=".">32.02</td>
<td align="char" char=".">34.19</td>
<td align="char" char=".">72.25</td>
<td align="char" char=".">34.19</td>
<td align="char" char=".">13.72</td>
<td align="char" char=".">45.18</td>
<td align="char" char=".">107.22</td>
</tr>
<tr>
<td rowspan="4" align="left">P-PO<sub>4</sub> [mg&#x2219;dm<sup>&#x2212;3</sup>]</td>
<td align="left">Range</td>
<td align="char" char=".">0.05&#x2013;0.54</td>
<td align="char" char=".">0.13&#x2013;0.62</td>
<td align="char" char=".">0.07&#x2013;0.38</td>
<td align="char" char=".">0.05&#x2013;0.54</td>
<td align="char" char=".">0.31&#x2013;0.62</td>
<td align="char" char=".">0.07&#x2013;0.38</td>
<td align="char" char=".">0.08&#x2013;0.22</td>
<td align="char" char=".">0.13&#x2013;0.55</td>
<td align="char" char=".">0.11&#x2013;0.26</td>
</tr>
<tr>
<td align="left">Average</td>
<td align="char" char=".">0.18</td>
<td align="char" char=".">0.36</td>
<td align="char" char=".">0.17</td>
<td align="char" char=".">0.19</td>
<td align="char" char=".">0.41</td>
<td align="char" char=".">0.17</td>
<td align="char" char=".">0.16</td>
<td align="char" char=".">0.29</td>
<td align="char" char=".">0.16</td>
</tr>
<tr>
<td align="left">SD</td>
<td align="char" char=".">0.10</td>
<td align="char" char=".">0.11</td>
<td align="char" char=".">0.06</td>
<td align="char" char=".">0.11</td>
<td align="char" char=".">0.07</td>
<td align="char" char=".">0.06</td>
<td align="char" char=".">0.05</td>
<td align="char" char=".">0.10</td>
<td align="char" char=".">0.16</td>
</tr>
<tr>
<td align="left">V</td>
<td align="char" char=".">57.33</td>
<td align="char" char=".">29.69</td>
<td align="char" char=".">36.38</td>
<td align="char" char=".">60.67</td>
<td align="char" char=".">16.88</td>
<td align="char" char=".">37.79</td>
<td align="char" char=".">28.51</td>
<td align="char" char=".">35.83</td>
<td align="char" char=".">99.31</td>
</tr>
</tbody>
</table>
</table-wrap>
<fig id="F3" position="float">
<label>FIGURE 3</label>
<caption>
<p>Spatial variability of: <bold>(A)</bold> total nitrogen; <bold>(B)</bold> nitrite nitrogen; <bold>(C)</bold> nitrate nitrogen; <bold>(D)</bold> ammonium nitrogen in the waters of the G&#x142;uszynka river in the hydrological years 2016&#x2013;2018.</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g003.tif"/>
</fig>
<fig id="F4" position="float">
<label>FIGURE 4</label>
<caption>
<p>Average contents of <bold>(A)</bold> total nitrogen; <bold>(B)</bold> nitrite nitrogen; <bold>(C)</bold> nitrate nitrogen; in the waters of the G&#x142;uszynka river in the hydrological years 2016&#x2013;2018, with the inflection point indicated.</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g004.tif"/>
</fig>
<p>The second element influencing the eutrophication process is phosphorus. Two forms of this element were analysed in this study: total phosphorus and orthophosphate phosphorus. The content of total phosphorus in the river waters during the studied years ranged from 0.08 to 1.76&#xa0;mg&#xa0;P&#xa0;dm<sup>&#x2212;3</sup>. The lowest mean value of this parameter was observed at sp G5 (0.32&#xa0;mg&#xa0;P&#xa0;dm<sup>&#x2212;3</sup>), and the highest mean value was recorded at sp G1 (0.44&#xa0;mg&#xa0;P&#xa0;dm<sup>&#x2212;3</sup>), below Lake Raczy&#x144;skie. High contents of orthophosphate phosphorus were observed in the G&#x142;uszynka river, ranging from 0.05&#xa0;mg&#xa0;P-PO<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup> to 0.62&#xa0;mg&#xa0;P-PO<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup>. The lowest mean value of this parameter was recorded at point G6 (0.246&#xa0;mg&#xa0;P-PO<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup>), and the highest mean value was recorded at point G1 (0.288&#xa0;mg&#xa0;P-PO<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup>). Along the course of the river the quality of water improved with respect to the abovementioned indices. For orthophosphate phosphorus a 14% reduction was observed between sampling points G1 and G7 (G1&#x2014;0.29 to G7&#x2014;0.25&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>) and for total phosphorus a 15.9% reduction was observed (G1&#x2014;0.44 to G7&#x2014;0.37&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>) (<xref ref-type="fig" rid="F5">Figures 5A,B</xref>). In the case of total phosphorus, the analysis of parametric statistical change point analysis showed no statistically significant change in the mean values of this indicator. However, it was detected in the case of orthophosphates. A statistically significant change in the content of this anion occurred between G3 and G4 sites (<xref ref-type="fig" rid="F6">Figure 6</xref>). In the lower sections of the river, lower mean values were observed in the case of orthophosphate phosphorus (V).</p>
<fig id="F5" position="float">
<label>FIGURE 5</label>
<caption>
<p>Spatial variability of the content of <bold>(A)</bold> orthophosphate phosphorous; <bold>(B)</bold> total phosphorus in the waters of the G&#x142;uszynka river during the hydrological years 2016&#x2013;2018.</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g005.tif"/>
</fig>
<fig id="F6" position="float">
<label>FIGURE 6</label>
<caption>
<p>Average content of orthophosphate phosphorous in the waters of the G&#x142;uszynka river during hydrological years 2016&#x2013;2018, with the inflection point indicated. Temporal variability of the content of nitrogen and phosphorus and their forms.</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g006.tif"/>
</fig>
<p>The content of total nitrogen showed high variability (CV &#x3d; 58.11%) during the research period. The maximum content of total nitrogen was observed at sp G5 (9.32&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup>, April 2018), located below Lake K&#xf3;rnickie (<xref ref-type="table" rid="T2">Table 2</xref>). Analyzing the annual mean content of total nitrogen, an increasing trend was observed for this parameter. The highest content of this element, 3.76&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup>, was observed in the hydrological 2018&#xa0;years and was higher than the average annual content of this parameter by 44.9% compared to the hydrological year 2016. The highest variability of this parameter was observed in the hydrological year 2017 (CV &#x3d; 66.42%). Also, the concentration of mineral forms of nitrogen (N-NO<sub>3</sub>, N-NO<sub>2</sub> and N-NH<sub>4</sub>) showed high variability (CV &#x3d; 78.57, 58.70 and 63.06%, respectively) in the analysed period. The highest content of N-NO<sub>3</sub> was recorded at sp G5 (6.95&#xa0;N-NO<sub>3</sub>&#xa0;dm<sup>&#x2212;3</sup>, April 2018). In the case of this form of mineral nitrogen (N-NO<sub>3</sub>), an increasing trend of its content was observed in successive research years. In the last analysed hydrological year, the content of this indicator was higher by 70.7% higher compared to the hydrological year 2016. However, the highest value of the coefficient of variation, 89.4%, was observed in the hydrological year 2017. For the nitrate nitrogen form (III), the highest value was recorded at sp G6 (0.44&#xa0;mg&#xa0;N-NO<sub>2</sub>&#xa0;dm<sup>&#x2212;3</sup>, March 2017), while for ammonium nitrogen, it was recorded in May 2016, at sp G2 (0.41&#xa0;mg&#xa0;N-NH<sub>4</sub>&#xa0;dm<sup>&#x2212;3</sup>). The content of these forms of mineral nitrogen (N-NO<sub>2</sub> and N-NH<sub>4</sub>) did not show a visible trend of changes in the successive research years. However, as for the previous forms of nitrogen, the highest variability of N-NO<sub>2</sub> was recorded in 2017 (CV &#x3d; 61.75%). For the ammonium form only, higher variability was recorded in 2016 (70.9%).</p>
<p>The analyzed forms of phosphorus showed different variability. Also for total phosphorus, the highest variability of the content was observed in the hydrological year 2017, which was 67.3%. It was also the year in which the highest values for this parameter were recorded (0.08&#x2013;1.76 mgP&#xa0;dm<sup>&#x2212;3</sup>). In comparison to nitrogen, no significant changes were observed between the analyzed years for total phosphorus. A slightly different pattern was observed for orthophosphate phosphorous, for which the highest variability in content was observed in 2016 (CV &#x3d; 57.3%), although much higher concentrations of this form of phosphorus were recorded in 2017 (<xref ref-type="table" rid="T2">Table 2</xref>).</p>
<p>One hypothesis put forward in the study assumes a significant influence of primary producers on the content of total nitrogen and its mineral forms in river waters. The results obtained for total nitrogen and nitrate nitrogen in the growing period were statistically significantly lower than for the non-vegetation period (<italic>p</italic> &#x3d; 0.05) (<xref ref-type="fig" rid="F7">Figure 7</xref>). In the growing period, the average content of nitrate nitrogen was 135% lower than in the non-vegetation period, and for total nitrogen 92% lower. However, for other mineral forms of nitrogen (N-NO<sub>2</sub> and N-NH<sub>4</sub>), no statistically significant differences were observed between the separate periods. The analysis of the temporal variability of the content of total phosphorus and orthophosphate phosphorus confirmed that there were no significant differences between these periods. However, for orthophosphate phosphorous (V), higher concentrations of this ion were recorded during the growing period, especially in the hydrological year 2017, by 41%.</p>
<fig id="F7" position="float">
<label>FIGURE 7</label>
<caption>
<p>Total nitrogen and phosphorous concentration vs. air temperature during hydrological years 2016&#x2013;2018.</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g007.tif"/>
</fig>
<p>The biogenic conditions in the river were characterized in this study based on the content of nitrogen and total phosphorus and their mineral forms. According to the Regulation of the Minister of Infrastructure, these parameters classified the ecological status of the waters of the G&#x142;uszynka river as below &#x201c;good,&#x201d; with the exception of ammonium nitrogen content, which met the threshold value for first class surface water quality (&#x2264;0.12&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>). The assessment of biological elements on the basis of phytoplankton, chlorophyll a, phytobenthos and macrophyte indexes conducted for the lakes of the K&#xf3;rnik-Zaniemyska Gutter by WIO&#x15a; in Pozna&#x144; (2011&#x2013;2018) classified waters of these lakes as &#x201c;poor.&#x201d; Taking into account the information on biological parameters of the analyzed river-lake system, the ecological status of the waters of the G&#x142;uszynka river were classified as &#x201c;poor.&#x201d;</p>
</sec>
</sec>
<sec sec-type="discussion" id="s4">
<title>Discussion</title>
<p>In this study, an attempt was made to determine the variability of phosphorus and nitrogen content and their mineral forms in the waters of the river-lake system of the G&#x142;uszynka river, both in temporal and spatial terms. The results of the river water quality analysis obtained were compared to the mode of catchment management and the activity of primary producers.</p>
<p>In the discussed river-lake system, trends in the analyzed parameters with the course of the river were observed. In the case of total nitrogen and its mineral forms, an increase in their content was observed in successive sampling points. On the other hand, for total phosphorus and orthophosphate phosphorus, a decrease in the values of those parameters was noted along with the course of the river. The results obtained indicate the heterogeneous role of lakes in this system. In the case of phosphorus, lake basins probably accumulated phosphorus and thus the quality of waters flowing out of them improved. As regards nitrogen, the more mobile element, the inflow of its additional loads to lakes, including adjacent agricultural areas and tourist activity, resulted in deterioration of surface water along with the course of the river. Similar results were obtained by <xref ref-type="bibr" rid="B44">Kuriata-Potasznik (2018)</xref>, who noted that lakes of river-lake systems can play an accumulation or transport role, depending on the morphometry and the size of loads introduced into the waters.</p>
<p>The ecological status of the waters of the G&#x142;uszynka river, due to the poor condition of both biological elements and physicochemical elements (the content of phosphorus and nitrogen compounds), was classified as &#x201c;poor.&#x201d; The only exception was ammonium nitrogen, on the basis of which the water of the river studied was classified as &#x201c;good&#x201d; (except for two measurement dates). The values of the coefficient of variation indicate high temporal variability of the parameters studied, which may result from the changing meteorological conditions, the activity of primary producers and the variable magnitude of anthropogenic pressure over time. This may explain the highest values of the coefficients of variation observed for 2017. It was a very wet year with an incident of torrential rain (July 2017), which caused a significant inflow of nutrients to the waters of the G&#x142;uszynka river (<xref ref-type="bibr" rid="B31">Iital et al., 2014</xref>; <xref ref-type="bibr" rid="B54">&#xd8;ygarden et al., 2014</xref>; <xref ref-type="bibr" rid="B53">Nausch et al., 2017</xref>; <xref ref-type="bibr" rid="B50">Matej-Lukowicz et al., 2020</xref>) (<xref ref-type="sec" rid="s11">Supplementary Figure S1</xref>).</p>
<p>The highest contents of total nitrogen and its mineral forms were observed in spring, which could indicate the transport of pollutants from nearby arable lands from drainage water, surface runoff, and groundwater. Similar results were obtained by <xref ref-type="bibr" rid="B37">Kneis et al. (2006)</xref>, who observed the highest nitrogen content in early spring and a reduction of this parameter in the following months. Also <xref ref-type="bibr" rid="B4">Bhat et al. (2014)</xref> analyzing the river-lake system of the Skuhang river, observed a similar trend of temporal changes in relation to nitrite and nitrate nitrogen. The lower content of total nitrogen observed in the waters of the G&#x142;uszynka river during the growing period (on average by 48.85%) was probably related to the activity of primary producers and intensive photosynthesis. A similar trend was also observed for nitrate nitrogen, while in the case of ammonium nitrogen and nitrite nitrogen no differences were found between the growing and non-vegetative periods. This could be explained by the bioavailability (<xref ref-type="bibr" rid="B29">Haynes and Goh, 1978</xref>; <xref ref-type="bibr" rid="B46">Lewi, 1986</xref>; <xref ref-type="bibr" rid="B38">Kobus, 1996</xref>) of particular mineral forms of nitrogen. Only nitrate nitrogen and ammonium nitrogen could be assimilated by primary producers. Hence, no differences were observed between these periods for the nitrite form. In the analysed period the waters of the G&#x142;uszynka river were characterised by conditions favourable to nitrification processes, which led to rapid oxidation of ammonium to nitrate forms, which could result in a lack of observed variation between these periods (<xref ref-type="bibr" rid="B76">Van Loon and Duffy, 2007</xref>). The analyzed area was classified as especially vulnerable to agricultural nitrate pollution. The variability of nitrogen content in surface water may also have been influenced by groundwater. <xref ref-type="bibr" rid="B63">Rosi&#x144;ska and Go&#x142;dyn (2018)</xref>, analyzing the specific conditions of one of the lakes of the K&#xf3;rnik-Zaniemyska Gutter, reported that the external load reached the lake mainly with the gradual and delayed inflow of groundwater from soils polluted by sewage from leaky septic tanks in the past.</p>
<p>For both total phosphorus and orthophosphate phosphorus, no statistically significant differences were recorded in their contents between the analyzed periods. During the growing period, higher concentrations of total phosphorus were observed at four sampling points (G1, G4, G6 and G7), which could be related to the transport of this nutrient with surface runoff. Determination of available phosphorus content in soils along with soil texture conducted for soil samples collected from shores and banks supports this assumption. Soils of the analysed river-lake system were characterized mostly by loamy sand texture or coarser, which are easily permeable formations with low retention capacity. In combination with a high and a very high content of available phosphorus in these soils (6.74&#x2013;20.95&#xa0;mg&#xa0;P100g<sup>&#x2212;1</sup>), favourable conditions for fast transport of phosphorus to surface waters were created. Municipal wastewater from the catchment area of the analysed river is directed to the wastewater treatment plants in town: Jeziory Ma&#x142;e, Bor&#xf3;wiec and Pozna&#x144;. Due to the lack of a chemical treatment stage, the treated wastewater discharged into the river is characterized by a high phosphorus load. According to the report made available by the treatment plants, the treated wastewater discharged into the analysed river contains up to 15&#xa0;mg&#xa0;N&#xa0;dm<sup>&#x2212;3</sup> for total nitrogen and up to 2&#xa0;mg&#xa0;P&#xa0;dm<sup>&#x2212;3</sup> for phosphorus. At the same time, the lack of clear seasonal differences in the phosphorus content in waters could also be related to the inflow of phosphorus loads from tourist and recreational activities, which in turn compensated for phosphorus assimilated by primary producers. According to <xref ref-type="bibr" rid="B63">Rosi&#x144;ska and Go&#x142;dyn (2018)</xref>, approximately 8,000 people in total use the bathing areas in the summer.</p>
<p>In addition, a PCA analysis between lake catchment land use and mean nutrient contents in water was performed in this study. This analysis explained 80.4% of the variability of the data. The first factor, which accounted 58.16% of data variability, was mainly related to the values of positively correlated indices such as: total nitrogen, nitrite and nitrate nitrogen. These indicators were negatively correlated with the content of total phosphorus. The above-mentioned indicators were mainly related to the agricultural land cover, which according to CLC2018 were designated as 231 (pastures) and311 (broad-leaved forest). The second factor, accounting for 22.24% of the variability in the data, was associated with ammonium nitrogen content in water, the content of which was negatively correlated with orthophosphate phosphate (V) content (<xref ref-type="fig" rid="F8">Figures 8A,B</xref>). Ammonium nitrogen content was associated with coniferous forest areas (312) and urbanized areas (112) (<xref ref-type="bibr" rid="B14">CLC, 2018</xref>; <xref ref-type="sec" rid="s11">Supplementary Figure S2</xref>).</p>
<fig id="F8" position="float">
<label>FIGURE 8</label>
<caption>
<p>Analysis of the main components of the physicochemical parameters of the G&#x142;uszynka river water in relation to: <bold>(A)</bold> use of the catchment area of the K&#xf3;rnik-Zaniemyska Gutter; <bold>(B)</bold> measurement points of the G&#x142;uszynka river downstream of the lakes (112&#x2014;Discontinuous urban fabric; 121&#x2014;Industrial or commercial units; 211&#x2014;Non-irrigated arable land; 231&#x2014;Pastures; 242&#x2014;Complex cultivation patterns; 243&#x2014;Land principally occupied by agriculture, with significant areas of natural vegetation; 311&#x2014;Broad-leaved forest; 312&#x2014;Coniferous forests; 313&#x2014;Mixed forest; 324&#x2014;Transitional woodland-shrub; 512&#x2014;Water bodies).</p>
</caption>
<graphic xlink:href="fenvs-10-874754-g008.tif"/>
</fig>
<p>The PCA analysis showed that the agricultural areas had the greatest impact on the increase in total nitrogen, N-NO<sub>3</sub> and N-NO<sub>2</sub> values. This was confirmed by the analysis of variability of these parameters. The greatest changes in the content of total nitrogen and nitrate nitrogen were observed at the G5, G6 and G7 sampling points, which are located below the lakes with a typically agricultural character of the catchment area. A significant change in the values of these parameters was confirmed by the analysis of the parametric statistical change point, which indicated that the inflection point was at sp G4, below Lake Bni&#x144;skie. It is the largest lake of this system with a typically agricultural catchment, which probably contributed to higher inflows of this element to surface waters. Also other lakes in the studied system were characterized by a significant share of agricultural land in the catchment area. It is likely that fertiliser materials used in agriculture increased the amount of mobile nitrogen forms, resulting in significantly higher nitrogen concentration in further sections of the river. Taking into account the fact that nitrogen is not subject to significant abiotic sorption processes and does not tend to precipitate as inorganic salts, the increased amounts of this element flowing from the catchment areas resulted in an increase in its concentration in the river waters. <xref ref-type="bibr" rid="B73">Tong et al. (2019)</xref> in their study on the variability of total nitrogen and phosphorus in water bodies highlighted the association of parameter variability with the location of the water bodies and anthropogenic factors. Similar conclusions were reached by <xref ref-type="bibr" rid="B66">Sobolewski et al. (2014)</xref>, who reported that as the proportion of land used for agriculture increased, surface water quality deteriorated. Also, studies conducted by <xref ref-type="bibr" rid="B7">Burzy&#x144;ska (2016)</xref> and <xref ref-type="bibr" rid="B8">Burzy&#x144;ska (2019)</xref> indicate a significant influence of agricultural areas on the quality of surface waters. The worst quality of surface water was observed for samples collected from the vicinity of arable land and agricultural buildings. Similarly, <xref ref-type="bibr" rid="B49">Lossow et al. (2006)</xref>, in a study on the Mar&#xf3;zka river-lake system, flowing through Mar&#xf3;z lake, in the catchment area of which arable land constitutes 60%, also observed deterioration in the quality of water in terms of nitrogen. The total nitrogen content below the reservoir was 6% higher. A study conducted on the Skuhang river (<xref ref-type="bibr" rid="B4">Bhata et al., 2014</xref>) also identified agricultural activities, including excessive and incompetent use of fertilizers and pesticides along with unregulated water and sewage management, as the main causes of poor quality of surface water.</p>
<p>Many studies conducted on river-lake systems have detected an increase in the content of ammonium nitrogen along with the course of the river. <xref ref-type="bibr" rid="B44">Kuriata-Potasznik (2018)</xref> in the Symsarna river-lake system observed an increase in ammonium nitrogen by 44.1%, which was explained by the occurrence of the denitrification process. On the other hand, the research conducted by <xref ref-type="bibr" rid="B7">Burzy&#x144;ska (2016)</xref> on the Raszynka river showed an increase in the content of ammonium nitrogen along with the course of the river, and the relationship between the intensity of rural and suburban development and municipal sewage discharges into the river was identified as the cause. No statistically significant changes (<italic>p</italic> &#x2264; 0.05) in the content of ammonium nitrogen along the river course were observed in the studied system. The analyzed catchment of the G&#x142;uszynka river is located in a suburban area, where the percentage of the catchment area with sewers does not exceed 61%. However, despite the high presence of urbanized areas in individual lake catchments (Bni&#x144;skie, K&#xf3;rnickie, Skrzynki Du&#x17c;e lakes), it did not significantly affect the quality of the waters.</p>
<p>A completely different trend of total nitrogen changes with the river course was reported by <xref ref-type="bibr" rid="B2">Andersen (1994)</xref>, <xref ref-type="bibr" rid="B16">Cook et al. (2010)</xref> and <xref ref-type="bibr" rid="B78">Wang et al. (2020)</xref>. For the Danish Guedeny river-lake system, which has a typically agricultural catchment (78% arable land), a 46% reduction in total nitrogen was observed, mainly due to the denitrification process in lakes (<xref ref-type="bibr" rid="B2">Andersen 1994</xref>). <xref ref-type="bibr" rid="B16">Cook et al. (2010)</xref> ) in a study on the Australian river-lake system of the Murray river, observed a reduction of total nitrogen with the course of the river by 7%. They associated this observation with processes occurring in the basin of Alexandrina and Albert, which are part of the river-lake system. <xref ref-type="bibr" rid="B78">Wang et al. (2020)</xref> found a 58% reduction in total nitrogen in the Yuxi river in China as a result of water flow through Chaochu lake. In the river-lake system of the G&#x142;uszynka river, the total nitrogen content probably did not decrease with the course of the river as there were unfavourable conditions for the denitrification process. In the analysed river-lake system seven lakes are non-stratified reservoirs characterised by year-round overturn. As a result, the oxygen content was too high for the denitrification process to have a significant effect on the total nitrogen content in the surface waters of the studied river-lake system.</p>
<p>The waters of the analysed river-lake system were characterised by high contents of both total phosphorus (up to 1.76&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>) and orthophosphate phosphorous (0.05&#x2013;0.62&#xa0;mg&#xa0;dm<sup>&#x2212;3</sup>), which classified them into an ecological status below &#x201c;good.&#x201d; The highest content of total phosphorus was observed at sp G6, located downstream of Skrzynki Du&#x17c;e lake with a large share of agricultural land in the catchment area, and at sp G1, located downstream of holiday resorts and numerous summer cottages around Lake Raczy&#x144;skie. High contents of this nutrient in the river-lake system of the G&#x142;uszynka river could have been caused by sewage discharges from nearby farms and surface run-off from nearby arable lands and recreational loads on the catchment area. The analysis of available phosphorus content in soils of the lakeshore supports these assumptions. In the majority of soils the abundance of this element was high or very high, which, combined with the coarse texture of these soils, creates favourable conditions for its transport (leaching) to surface waters (<xref ref-type="sec" rid="s11">Supplementary Table S1</xref>) (<xref ref-type="bibr" rid="B79">Wiatrowska and Komisarek, 2015</xref>). During the study, the highest total phosphorus contents in the river waters were observed in months with the highest rainfall totals exceeding 150&#xa0;mm (<xref ref-type="bibr" rid="B32">Janicka 2020</xref>). The river-lake system studied is located in a sewered area, but in the catchment boundary, there are still many leaking cesspits (underground sealed tanks) (<xref ref-type="bibr" rid="B71">The Local Data Bank, 2020</xref>).</p>
<p>Analyzing the spatial variability of the content of total phosphorus and orthophosphate phosphorous along with the river flow through the lakes, there was a decrease of P by 15.9% and P-PO<sub>4</sub> by 14%. However, in the case of sampling points G4 and G6, due to the agricultural nature of the catchment area of the Bni&#x144;skie and Skrzynki Du&#x17c;e lakes, increases in the total phosphorus value were observed at these points. The obtained results contradicted the hypothesis that with a longer residence time of the water in the lake the content of phosphorus and its forms in the water body would decrease as a result of the sorption and precipitation processes. It is possible that these results were strongly influenced by the catchment land usage. In the case of the two lakes with the longest water exchange period (Bni&#x144;skie (G4) and Skrzynki Du&#x17c;e (G6)), the proportion of agricultural land exceeded 75% of the catchment area. In the case of orthophosphate phosphorus, higher values were observed at sp G3, below Lake Jeziory Wielkie, which could have been caused by the inflow of treated sewage from the municipal sewage treatment plant. The positive impact of the lakes on the water quality of the G&#x142;uszynka river in terms of the P-PO<sub>4</sub> content is confirmed by the parametric statistical change point analysis. The results of this analysis indicate significantly lower mean values of the orthophosphate phosphorus below sp G3. Similar results were obtained by <xref ref-type="bibr" rid="B60">Potasznik et al. (2014)</xref> in the Symsarna river catchment area, which confirmed the positive impact of lakes on the river quality in terms of total phosphorus content. As a result of the river flowing through lakes, the content of this element decreased by nearly 28%. At the same time, they observed that a decrease in the content of orthophosphate phosphorous occurred only during the growing period, when it was taken up by primary producers. Similar conclusions were reached by <xref ref-type="bibr" rid="B65">Sobczy&#x144;ska-W&#xf3;jcik and Rafa&#x142;owska (2011)</xref>, who conducted research on the water quality of the river-lake system of the S&#x119;tal river, where they observed a 36% reduction in total phosphorus content in the river. <xref ref-type="bibr" rid="B49">Lossow et al. (2006)</xref> analyzing the river-lake systems of the Mar&#xf3;zka and &#x141;yna rivers, also detected a beneficial effect of the lakes on river water quality, where the phosphorus load on the river was reduced by 10.1%. Similarly, <xref ref-type="bibr" rid="B16">Cook et al. (2010)</xref> in a study on the Australian river-lake system of the Murray river and <xref ref-type="bibr" rid="B78">Wang et al. (2020)</xref> on the Yuxi river observed the phenomenon of total phosphorus retention in lake waters, which resulted in a 48% reduction in the content of this element in river waters. The phenomenon of reduction of phosphorus content in river-lake systems after water flow through lakes may be related, according to <xref ref-type="bibr" rid="B35">Kanclerz et al. (2015)</xref> and <xref ref-type="bibr" rid="B32">Janicka (2020)</xref>, to the precipitation of insoluble forms of phosphate salts. As suggested by <xref ref-type="bibr" rid="B35">Kanclerz et al. (2015)</xref> and <xref ref-type="bibr" rid="B32">Janicka (2020)</xref>, accumulated phosphorus compounds in bottom sediments may be a secondary source of river water pollution under conditions favourable for P release from bottom sediments (low P-PO<sub>4</sub> concentrations).</p>
<p>The PCA analysis, taking into account the catchment use of the lakes and the content of analyzed nutrient forms, confirmed previous assumptions about the significant role of catchment management on surface water quality. The projection of sampling points at the G&#x142;uszynka river (<xref ref-type="fig" rid="F8">Figures 8A,B</xref>) indicated an influence of agricultural land (211, 242, 243) on the content of orthophosphate phosphorous and deciduous forests (311) on total phosphorus. The higher contents of total and P-PO<sub>4</sub> were strongly related to two sampling points G1 and G4. Sp G1, located downstream of Lake Raczy&#x144;skie, with a typically agricultural character of the catchment and a high tourist load, was most strongly related to the content of total phosphorus in the water, whereas sampling point G4 located below the Lake Bni&#x144;skie, with a typically agricultural catchment area was mostly related to orthophosphate phosphorus.</p>
</sec>
<sec sec-type="conclusion" id="s5">
<title>Conclusion</title>
<p>The water quality of river-lake systems is the result of several factors, including the structure of the catchment use, the seasonality of anthropopressure factors (e.g., agricultural activity and recreation) and the activity of living organisms. The ecological status of the waters of the G&#x142;uszynka river were classified as &#x201c;poor,&#x201d; due to a high load of nutrients from the catchment area as arable land reaches the shoreline of the lakes, strong tourist and recreational pressure, and incomplete sewerage in communities. The statistical analyses carried out showed that catchment use affects the amount of nutrients. Arable land contributed to an increase in the content of orthophosphate phosphorus, while grassland contributed to total nitrogen, nitrate and nitrite nitrogen. The urbanized areas were responsible for inflows of ammonium nitrogen. The content of nitrogen and its mineral forms in the G&#x142;uszynka surface waters were also related to both the period of the year and the agricultural works carried out at that time. The highest values of these parameters were observed in the spring, before the intensive period of plant growth. Along with the intensification of the photosynthesis process, the content of nitrogen and its compounds in surface waters decreased. Only the content of orthophosphate phosphorus increased during the growing period, which could be related to intensive recreational use of the lakes of the analyzed system. Analyzing the influence of the lakes on the water quality of the G&#x142;uszynka river, their negative influence was observed in terms of total nitrogen and its mineral forms, which increased along the course of the river. However, in the case of total phosphorus and orthophosphate phosphorus a reduction in the values of these indicators was observed, which was probably related to the process of accumulation of phosphorus compounds in bottom sediments that took place in reservoirs. The parametric statistical change point analysis carried out showed that sp G4, located below Lake Bni&#x144;skie, was a critical point for the water quality of the G&#x142;uszynka river.</p>
<p>The quality of surface waters depends on many factors, but in the case of cascade river-lake systems the situation becomes even more complicated due to the possible influence of bottom sediments on the chemistry of flowing waters. Therefore, the possibility of improving surface water quality, as required by the Water Framework Directive, in such systems requires further research that additionally takes into account the chemistry of lake bottom sediments</p>
</sec>
</body>
<back>
<sec id="s6">
<title>Data Availability Statement</title>
<p>The original contributions presented in the study are included in the article/<xref ref-type="sec" rid="s11">Supplementary Material</xref>, further inquiries can be directed to the corresponding author.</p>
</sec>
<sec id="s7">
<title>Author Contributions</title>
<p>EJ, JK and KW conceived and designed this study. EJ performed the field trip, sample analysis and data analysis. EJ drafted the original manuscript. JK and KW provided comments. JK and KW provided the very constructive suggestion and revision. AB helped with the statistical analysis.</p>
</sec>
<sec id="s8">
<title>Funding</title>
<p>The publication was co-financed/financed within the framework of Ministry of Science and Higher Education programme as &#x201c;Regional Initiative Excellence&#x201d; in years 2019&#x2013;2022, Project No. 005/RID/2018/19.</p>
</sec>
<sec sec-type="COI-statement" id="s9">
<title>Conflict of Interest</title>
<p>The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.</p>
</sec>
<sec sec-type="disclaimer" id="s10">
<title>Publisher&#x2019;s Note</title>
<p>All claims expressed in this article are solely those of the authors and do not necessarily represent those of their affiliated organizations, or those of the publisher, the editors, and the reviewers. Any product that may be evaluated in this article, or any claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
<ack>
<p>I would like to thank the Department of Land Improvement, Environmental Development and Spatial Management for the opportunity to conduct the research.</p>
</ack>
<sec id="s11">
<title>Supplementary Material</title>
<p>The Supplementary Material for this article can be found online at: <ext-link ext-link-type="uri" xlink:href="https://www.frontiersin.org/articles/10.3389/fenvs.2022.874754/full#supplementary-material">https://www.frontiersin.org/articles/10.3389/fenvs.2022.874754/full&#x23;supplementary-material</ext-link>
</p>
<supplementary-material xlink:href="DataSheet1.PDF" id="SM1" mimetype="application/PDF" xmlns:xlink="http://www.w3.org/1999/xlink"/>
</sec>
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