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<front>
<journal-meta>
<journal-id journal-id-type="publisher-id">Front. Water</journal-id>
<journal-title>Frontiers in Water</journal-title>
<abbrev-journal-title abbrev-type="pubmed">Front. Water</abbrev-journal-title>
<issn pub-type="epub">2624-9375</issn>
<publisher>
<publisher-name>Frontiers Media S.A.</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="doi">10.3389/frwa.2024.1369552</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Water</subject>
<subj-group>
<subject>Original Research</subject>
</subj-group>
</subj-group>
</article-categories>
<title-group>
<article-title>Insights gained from two decades of intensive monitoring: hydrology and nitrate export in a tile-drained agricultural catchment</article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author" corresp="yes">
<name><surname>Bauwe</surname> <given-names>Andreas</given-names></name>
<xref ref-type="corresp" rid="c001"><sup>&#x002A;</sup></xref>
<uri xlink:href="https://loop.frontiersin.org/people/421431/overview"/>
<role content-type="https://credit.niso.org/contributor-roles/conceptualization/"/>
<role content-type="https://credit.niso.org/contributor-roles/formal-analysis/"/>
<role content-type="https://credit.niso.org/contributor-roles/methodology/"/>
<role content-type="https://credit.niso.org/contributor-roles/writing-original-draft/"/>
</contrib>
<contrib contrib-type="author">
<name><surname>Lennartz</surname> <given-names>Bernd</given-names></name>
<uri xlink:href="https://loop.frontiersin.org/people/89460/overview"/>
<role content-type="https://credit.niso.org/contributor-roles/conceptualization/"/>
<role content-type="https://credit.niso.org/contributor-roles/supervision/"/>
<role content-type="https://credit.niso.org/contributor-roles/writing-review-editing/"/>
</contrib>
</contrib-group>
<aff><institution>Faculty of Agricultural and Environmental Sciences, University of Rostock</institution>, <addr-line>Rostock</addr-line>, <country>Germany</country></aff>
<author-notes>
<fn fn-type="edited-by" id="fn0002">
<p>Edited by: Qian Zhang, University of Maryland, College Park, United States</p>
</fn>
<fn fn-type="edited-by" id="fn0003">
<p>Reviewed by: Elisa Soana, University of Ferrara, Italy</p>
<p>Mar&#x00ED;a Luz Rodr&#x00ED;guez, University of A Coru&#x00F1;a, Spain</p>
</fn>
<corresp id="c001">&#x002A;Correspondence: Andreas Bauwe, <email>andreas.bauwe@uni-rostock.de</email></corresp>
</author-notes>
<pub-date pub-type="epub">
<day>15</day>
<month>04</month>
<year>2024</year>
</pub-date>
<pub-date pub-type="collection">
<year>2024</year>
</pub-date>
<volume>6</volume>
<elocation-id>1369552</elocation-id>
<history>
<date date-type="received">
<day>12</day>
<month>01</month>
<year>2024</year>
</date>
<date date-type="accepted">
<day>04</day>
<month>04</month>
<year>2024</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright &#x00A9; 2024 Bauwe and Lennartz.</copyright-statement>
<copyright-year>2024</copyright-year>
<copyright-holder>Bauwe and Lennartz</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>Nitrate (NO<sub>3</sub><sup>&#x2212;</sup>) export from agricultural land poses an ongoing threat to both inland and coastal waters. Experimental studies investigating the hydrology-NO<sub>3</sub><sup>&#x2212;</sup>-export mechanisms require long-term data to identify reliable causal relationships. In this study, utilizing a 23-year continuous dataset with a high temporal resolution (daily to twice a week), we aim to identify potential drivers for NO<sub>3</sub>-losses and assess the impact of nitrogen (N) soil surface budgets on NO<sub>3</sub>-export. A drainage plot (4.2&#x2009;ha) and a ditch catchment (179&#x2009;ha) were fully equipped to register hydrological parameters, including water sample collection. Mean annual NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations (loads) for the drainage plot and the ditch catchment were 9.4&#x2009;mg&#x2009;l<sup>&#x2212;1</sup> (20.6&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>) and 6.0&#x2009;mg&#x2009;L<sup>&#x2212;1</sup> (20.9&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>), respectively. Annual discharge was closely positively correlated with annual NO<sub>3</sub>-losses, highlighting the significant influence of prevailing weather and, consequently, hydrologic conditions on NO<sub>3</sub>-export rates. The majority of the annual NO<sub>3</sub><sup>&#x2212;</sup>-load was exported during winter (56% at the drainage plot, 51% at the ditch catchment), while the rest was exported during spring (28, 29%), summer (9, 9%) and fall (7, 11%). We could not find any direct relationships between N soil surface budgets and NO<sub>3</sub>-losses. Putting all results together, it can be concluded that agricultural activities for many decades resulted in high soil N stocks, which determined the general high NO<sub>3</sub><sup>&#x2212;</sup>-N concentration levels. Nevertheless, temporal NO<sub>3</sub>-export dynamics during the last two decades were clearly driven by hydro-meteorological conditions, nearly independently of land management and N soil surface budgets on the fields.</p>
</abstract>
<kwd-group>
<kwd>agriculture</kwd>
<kwd>nitrate</kwd>
<kwd>nitrogen</kwd>
<kwd>long-term monitoring</kwd>
<kwd>soil surface budget</kwd>
<kwd>tile drainage agriculture</kwd>
<kwd>tile drainage</kwd>
</kwd-group>
<counts>
<fig-count count="8"/>
<table-count count="1"/>
<equation-count count="2"/>
<ref-count count="51"/>
<page-count count="10"/>
<word-count count="6526"/>
</counts>
<custom-meta-wrap>
<custom-meta>
<meta-name>section-at-acceptance</meta-name>
<meta-value>Environmental Water Quality</meta-value>
</custom-meta>
</custom-meta-wrap>
</article-meta>
</front>
<body>
<sec sec-type="intro" id="sec1">
<label>1</label>
<title>Introduction</title>
<p>Nutrient export from agricultural land is continuing to threaten our inland and coastal waters. To achieve a good ecological status for surface water bodies, numerous directives and action plans have been established at both the European Union level (<xref ref-type="bibr" rid="ref18">EC, 1991</xref>, <xref ref-type="bibr" rid="ref19">2000</xref>) and regionally (<xref ref-type="bibr" rid="ref41">OSPAR, 1992</xref>; <xref ref-type="bibr" rid="ref25">HELCOM, 2007</xref>). Nitrogen (N) pollution remains elevated and ecologically unacceptable in various regions worldwide (<xref ref-type="bibr" rid="ref49">UBA, 2018</xref>; <xref ref-type="bibr" rid="ref40">Oelsner and Stets, 2019</xref>; <xref ref-type="bibr" rid="ref51">Yu et al., 2019</xref>; <xref ref-type="bibr" rid="ref31">Malone and Newton, 2020</xref>).</p>
<p>Compelling evidence indicates that long-term N fertilizer application has resulted in soil N enrichment in numerous agricultural watersheds (<xref ref-type="bibr" rid="ref50">Van Meter et al., 2016</xref>; <xref ref-type="bibr" rid="ref2">Ascott et al., 2017</xref>; <xref ref-type="bibr" rid="ref9">Chen et al., 2018</xref>). Owing to positive N soil surface budgets, N enrichment in agricultural soils is likely to be continued in the near future. However, a modeling study examining the evolution of N surplus in Europe for more than a century identified a gradual decline in N surplus in European soils in the recent past (<xref ref-type="bibr" rid="ref4">Batool et al., 2022</xref>). The reasons for this decline are undoubtedly multifaceted, with administrative regulations playing a pivotal role. For instance, in its efforts to counteract excessive N export into surface water bodies, Germany has progressively tightened regulations concerning annual N surplus, reducing it from 90&#x2009;kg&#x2009;N&#x2009;ha<sup>&#x2212;1</sup> in 2006 to 50&#x2009;kg&#x2009;N&#x2009;ha<sup>&#x2212;1</sup> from 2018 onwards (<xref ref-type="bibr" rid="ref15">D&#x00FC;V, 1996</xref>, <xref ref-type="bibr" rid="ref16">2006</xref>, <xref ref-type="bibr" rid="ref17">2017</xref>). These administrative measures appear to be gradually having a positive effect on surface water quality. For example, there is a weak tendency of decreasing nitrate-nitrogen (NO<sub>3</sub><sup>&#x2212;</sup>-N) concentrations in German rivers (<xref ref-type="bibr" rid="ref001">BMUB, 2017</xref>). At European level, a decrease in NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations can be observed in some rivers (Rhine, Odense, Thames), while NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations continue to rise in other large rivers (e.g., Loire) (<xref ref-type="bibr" rid="ref002">Bouraoui and Grizzetti, 2011</xref>). The different trends were partially explained by different NO<sub>3</sub>-lag times (<xref ref-type="bibr" rid="ref002">Bouraoui and Grizzetti, 2011</xref>).</p>
<p>NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations and loads in streams are controlled by a variety of factors. One important factor is land use. For example, NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations are usually lower in forested catchments compared to agricultural catchments (<xref ref-type="bibr" rid="ref32">Mayer et al., 2002</xref>; <xref ref-type="bibr" rid="ref44">Poor and McDonnell, 2007</xref>; <xref ref-type="bibr" rid="ref3">Barnes and Raymond, 2010</xref>), in which N is added in form of mineral and/or organic fertilizers. Hydro-meteorological conditions also play a crucial role in driving NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations and export patterns in streams. Many studies have demonstrated a close positive correlation between discharge and NO<sub>3</sub><sup>&#x2212;</sup>-N loads (e.g., <xref ref-type="bibr" rid="ref48">Tomer et al., 2003</xref>; <xref ref-type="bibr" rid="ref6">Bauwe et al., 2020</xref>). <xref ref-type="bibr" rid="ref48">Tomer et al. (2003)</xref> reported for a tile-drained watershed in Iowa, USA, that NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations were not typically diluted by large flows resulting in high NO<sub>3</sub><sup>&#x2212;</sup>-N loads during discharge events. They concluded that practices to optimize N management within fields should be encouraged, because edge-of-field measures such as constructed wetlands cannot effectively remove NO<sub>3</sub><sup>&#x2212;</sup>-N during large flows (<xref ref-type="bibr" rid="ref48">Tomer et al., 2003</xref>). Furthermore, NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations often exhibit seasonal variations depending on discharge composition. An Austrian study has shown that alternating aquifer contributions within a year controlled to a large degree the seasonality of the NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations in the streams due to significantly higher NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations in the shallow aquifer compared to the deep aquifer (<xref ref-type="bibr" rid="ref20">Exner-Kittridge et al., 2016</xref>). At the event scale, NO<sub>3</sub><sup>&#x2212;</sup>-N concentration patterns present a nuanced picture, with scientific literature reporting both dilution effects (<xref ref-type="bibr" rid="ref26">Inamdar et al., 2004</xref>; <xref ref-type="bibr" rid="ref21">Feinson et al., 2016</xref>) and accretion effects (<xref ref-type="bibr" rid="ref24">Fu&#x010D;&#x00ED;k et al., 2012</xref>; <xref ref-type="bibr" rid="ref7">Bauwe et al., 2015</xref>).</p>
<p>A limited investigation period is often an obstacle in experimental studies to identify long-term trends or to uncover relations between hydrology and nitrate export patterns. In 2001, we fully equipped a 4.2&#x2009;ha drainage plot and a 179&#x2009;ha ditch catchment for the purpose of monitoring hydrological parameters, including water sample collection. The continuous monitoring effort has yielded a large continuous data set with a high temporal resolution (daily to twice a week) spanning over 22&#x2009;years (2001&#x2013;2022). Here, we use this extensive dataset to identify potential drivers for NO<sub>3</sub>-losses and investigate the impact of N soil surface budgets on NO<sub>3</sub>-export.</p>
</sec>
<sec sec-type="materials|methods" id="sec2">
<label>2</label>
<title>Materials and methods</title>
<sec id="sec3">
<label>2.1</label>
<title>Study site</title>
<p>The study area is situated in northeastern Germany, approximately 10&#x2009;km southeast of Rostock (<xref ref-type="fig" rid="fig1">Figure 1</xref>). Characterized by conventional arable use covering 94% of the region, the landscape features minimal forested areas, accounting for only 6%. The catchment is located in a glacially formed landscape with a flat topography and only gentle slopes (slope gradients &#x003C;3%). Mineral soils (mainly sandy loams) are characteristic for the area, with a predominance of Luvisols (48%), Gleysols (43%), and Stagnic Gleysols (9%). The four agricultural fields in the study area (<xref ref-type="fig" rid="fig1">Figure 1</xref>) are tile-drained with a drainage depth 1.1&#x2009;m and a drainage distance from 8 to 22&#x2009;m.</p>
<fig position="float" id="fig1">
<label>Figure 1</label>
<caption>
<p>Study area.</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g001.tif"/>
</fig>
<p>Water originating from the tile drains flows into a main ditch (<xref ref-type="fig" rid="fig1">Figure 1</xref>). The drainage plot (field 4) and the ditch catchment (including fields 1, 2, 3, 4) are 4.2&#x2009;ha and 179&#x2009;ha in size, respectively. Tile drain flow is most pronounced during the winter months, extending from November to April. This temporal pattern corresponds to a precipitation surplus attributable to lower temperatures and reduced evapotranspiration rates during this period. Mean annual precipitation was 614&#x2009;mm and the mean annual temperature was 9.1&#x00B0;C (2001&#x2013;2022). While precipitation is predominantly in the form of rainfall, certain winters experienced substantial snow cover, notably in 2009 and 2010. Due to the high areal proportion of tile drainage (94%), discharge in the ditch is mainly controlled by tile flow and groundwater flow (<xref ref-type="bibr" rid="ref5">Bauwe et al., 2016</xref>). In contrast, surface runoff is only sporadically being observed during intense storm events.</p>
</sec>
<sec id="sec4">
<label>2.2</label>
<title>Hydrological data</title>
<p>The sampling station positioned at the outlet of the drainage plot, linked to the collector drain, is equipped with a Venturi flume (RBC-flume, UGT GmbH, Germany). This apparatus enables continuous and automatic water level measurement at 15&#x2009;min intervals. The recorded water level data are subsequently converted into flow data at the collector drain through the application of regression equations supplied by the manufacturer. The sampling station at the ditch located at the catchment outlet is equipped with an automatic, ultrasonic, water level measurement device (Teledyne Isco, Inc., Lincoln, NE). We conducted frequent flow measurements, typically on a weekly basis, utilizing an inductive flowmeter (Flo-Mate TM, Marsh-McBirney, Inc., Frederick, MD) to develop rating curves for this station. Rating curves were used to calculate daily flow data using the automatic water level measurements.</p>
</sec>
<sec id="sec5">
<label>2.3</label>
<title>Nitrate data</title>
<p>Water samples from both the drainage plot and the ditch were systematically collected using ISCO samplers (Teledyne Isco, Inc., Lincoln, NE), typically a minimum of twice a week. After collecting the water samples, they were promptly transported to the laboratory and frozen at &#x2212;20&#x00B0;C to preserve their integrity until the subsequent analysis for NO<sub>3</sub><sup>&#x2212;</sup>-N. The analysis of NO<sub>3</sub><sup>&#x2212;</sup>-N was conducted through ion chromatography, utilizing equipment from Metrohm AG, Herisau, Switzerland. To derive daily, monthly and annual NO<sub>3</sub><sup>&#x2212;</sup>-N loads for both the drainage plot and the ditch catchment, we used the R software package <italic>RiverLoad</italic> (<xref ref-type="bibr" rid="ref39">Nava et al., 2019</xref>). This package provides different methods for load estimation, such as averaging methods, ratio estimators and regression methods. Based on our dataset with continuous flow data and instantaneous concentration data, load estimation using linear interpolation of concentration data was appropriate for this study:</p>
<disp-formula id="EQ1">
<label>(1)</label>
<mml:math id="M1">
<mml:mi>L</mml:mi>
<mml:mo>=</mml:mo>
<mml:msup>
<mml:mi>K</mml:mi>
<mml:mo>&#x2033;</mml:mo>
</mml:msup>
<mml:munderover>
<mml:mstyle displaystyle="true">
<mml:mo stretchy="true">&#x2211;</mml:mo>
</mml:mstyle>
<mml:mrow>
<mml:mi>j</mml:mi>
<mml:mo>=</mml:mo>
<mml:mn>1</mml:mn>
</mml:mrow>
<mml:mi>n</mml:mi>
</mml:munderover>
<mml:msubsup>
<mml:mi>C</mml:mi>
<mml:mi>j</mml:mi>
<mml:mtext>int</mml:mtext>
</mml:msubsup>
<mml:msub>
<mml:mi>Q</mml:mi>
<mml:mi>j</mml:mi>
</mml:msub>
</mml:math>
</disp-formula>
<p>where <italic>L</italic> is the NO<sub>3</sub><sup>&#x2212;</sup>-N load, <italic>C<sub>j</sub></italic><sup>int</sup> (g&#x2009;m<sup>&#x2212;3</sup>) is the daily NO<sub>3</sub><sup>&#x2212;</sup>-N concentration linearly interpolated between two measured samples, <italic>Q<sub>j</sub></italic> (m<sup>3</sup> s<sup>&#x2212;1</sup>) is the mean daily streamflow and <italic>K&#x2033;</italic> is a conversion factor for the period of load estimation (<xref ref-type="bibr" rid="ref37">Moatar and Meybeck, 2005</xref>).</p>
<p>It is pertinent to note that the annual values for both hydrological data and NO<sub>3</sub><sup>&#x2212;</sup>-N data pertain to a hydrologic year spanning from November to October.</p>
</sec>
<sec id="sec6">
<label>2.4</label>
<title>Nitrogen soil surface budget</title>
<p>Field records from the local farmer, encompassing detailed agricultural practices, served as the foundation for calculating annual N soil surface budgets from 2001 to 2022. The crop rotation during the investigation contained common crops such as winter wheat (<italic>Triticum aestivum</italic> L.), winter barley (<italic>Hordeum vulgare</italic> L.), rapeseed (<italic>Brassica napus</italic> L.), and maize (<italic>Zea mays</italic> L.) (<xref ref-type="table" rid="tab1">Table 1</xref>). Periodically, sugar beet (<italic>Beta vulgaris</italic> L.) and legumes such as peas (<italic>Pisum sativum</italic> L.) or alfalfa (<italic>Medicago sativa</italic> L.) were also cultivated. This crop rotation is typical for conventional arable farming in northern Germany. Annual N applications varied based on crop selection, as detailed in <xref ref-type="table" rid="tab1">Table 1</xref>. N fertilizers, primarily in mineral form, were applied three to four times a year. Winter wheat and winter barley were typically sown in the latter part of September and harvested in the subsequent summer. Rapeseed was sown about a month earlier, and its harvest coincided with that of winter wheat and winter barley. Maize, sugar beet, and peas were sown in late April and harvested in late summer or early fall of the same year. <xref ref-type="table" rid="tab1">Table 1</xref> additionally provides information on N in yields for the main crops.</p>
<table-wrap position="float" id="tab1">
<label>Table 1</label>
<caption>
<p>Main crops, N fertilization and N in yields.</p>
</caption>
<table frame="hsides" rules="groups">
<thead>
<tr>
<th align="left" valign="top" rowspan="2">Crop</th>
<th align="center" valign="top" colspan="4">Number of cropping years</th>
<th align="center" valign="top" rowspan="2">Fertilization (kg&#x2009;N&#x2009;ha<sup>&#x2212;1</sup>)</th>
<th align="center" valign="top" rowspan="2">N yield (kg&#x2009;N&#x2009;ha<sup>&#x2212;1</sup>)</th>
</tr>
<tr>
<th align="center" valign="top">Field 1</th>
<th align="center" valign="top">Field 2</th>
<th align="center" valign="top">Field 3</th>
<th align="center" valign="top">Field 4</th>
</tr>
</thead>
<tbody>
<tr>
<td align="left" valign="middle">Winter wheat</td>
<td align="center" valign="middle">6</td>
<td align="center" valign="middle">4</td>
<td align="center" valign="middle">5</td>
<td align="center" valign="middle">6</td>
<td align="char" valign="middle" char="&#x00B1;">214 &#x00B1; 22</td>
<td align="char" valign="middle" char="&#x00B1;">171 &#x00B1; 23</td>
</tr>
<tr>
<td align="left" valign="middle">Winter barley</td>
<td align="center" valign="middle">4</td>
<td align="center" valign="middle">3</td>
<td align="center" valign="middle">2</td>
<td align="center" valign="middle">1</td>
<td align="char" valign="middle" char="&#x00B1;">180 &#x00B1; 10</td>
<td align="char" valign="middle" char="&#x00B1;">153 &#x00B1; 14</td>
</tr>
<tr>
<td align="left" valign="middle">Rapeseed</td>
<td align="center" valign="middle">5</td>
<td align="center" valign="middle">4</td>
<td align="center" valign="middle">4</td>
<td align="center" valign="middle">5</td>
<td align="char" valign="middle" char="&#x00B1;">211 &#x00B1; 32</td>
<td align="char" valign="middle" char="&#x00B1;">150 &#x00B1; 21</td>
</tr>
<tr>
<td align="left" valign="middle">Maize silage</td>
<td align="center" valign="middle">6</td>
<td align="center" valign="middle">8</td>
<td align="center" valign="middle">5</td>
<td align="center" valign="middle">4</td>
<td align="char" valign="middle" char="&#x00B1;">135 &#x00B1; 50</td>
<td align="char" valign="middle" char="&#x00B1;">165 &#x00B1; 25</td>
</tr>
</tbody>
</table>
<table-wrap-foot>
<p>&#x00B1;Indicate standard deviations.</p>
</table-wrap-foot>
</table-wrap>
<p>N soil surface budget was calculated for all four fields in the catchment accounting for mineral and organic fertilization, N fixation, and harvest as follows:</p>
<disp-formula id="EQ2">
<label>(2)</label>
<mml:math id="M2">
<mml:msub>
<mml:mi mathvariant="normal">N</mml:mi>
<mml:mrow>
<mml:mi>s</mml:mi>
<mml:mi>u</mml:mi>
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</mml:mrow>
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<mml:mo>=</mml:mo>
<mml:msub>
<mml:mi mathvariant="normal">N</mml:mi>
<mml:mi mathvariant="italic">min</mml:mi>
</mml:msub>
<mml:mo>+</mml:mo>
<mml:msub>
<mml:mi mathvariant="normal">N</mml:mi>
<mml:mrow>
<mml:mi>o</mml:mi>
<mml:mi>r</mml:mi>
<mml:mi>g</mml:mi>
</mml:mrow>
</mml:msub>
<mml:mo>+</mml:mo>
<mml:msub>
<mml:mi mathvariant="normal">N</mml:mi>
<mml:mi mathvariant="italic">fix</mml:mi>
</mml:msub>
<mml:mo>+</mml:mo>
<mml:msub>
<mml:mi mathvariant="normal">N</mml:mi>
<mml:mi mathvariant="italic">atm</mml:mi>
</mml:msub>
<mml:mo>&#x2212;</mml:mo>
<mml:msub>
<mml:mi mathvariant="normal">N</mml:mi>
<mml:mrow>
<mml:mi>y</mml:mi>
<mml:mi>l</mml:mi>
<mml:mi>d</mml:mi>
</mml:mrow>
</mml:msub>
</mml:math>
</disp-formula>
<p>where N<sub>sur</sub> is N soil surface budget, N<sub>min</sub> is amount of N in mineral fertilizer, N<sub>org</sub> is amount of N in organic fertilizer accounting for ammonia volatilization, N<sub>fix</sub> is amount of N fixed by legumes, N<sub>atm</sub> is amount of atmospheric N deposition, and N<sub>yld</sub> is amount of N in harvested yield. All units are (kg&#x2009;ha<sup>&#x2212;1</sup>). Data on the N content of organic fertilizers, harvested crops, N fixation rates, and losses due to ammonia volatilization were sourced from literature (<xref ref-type="bibr" rid="ref34">MLUV-MV, 2008</xref>, <xref ref-type="bibr" rid="ref36">2019</xref>). The atmospheric N deposition was 14&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup> for the study catchment.<xref ref-type="fn" rid="fn0001"><sup>1</sup></xref> The N content of mineral fertilizers was obtained from manufacturer specifications. Fertilizer application details and crop yields for each field were provided by the farmer. Notably, the N soil surface budgets of the drainage plot align with those of field 4 (<xref ref-type="fig" rid="fig1">Figure 1</xref>), while those of the ditch catchment were computed as area-weighted means of the four fields within the catchment.</p>
</sec>
</sec>
<sec sec-type="results" id="sec7">
<label>3</label>
<title>Results and discussion</title>
<sec id="sec8">
<label>3.1</label>
<title>Flow regime and nitrate concentrations</title>
<p>Streamflow and NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations at both the collector drain and the ditch exhibited pronounced dynamics throughout the study period (<xref ref-type="fig" rid="fig2">Figure 2</xref>). Peak flows and maximum annual NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations predominantly occurred during the winter, while both streamflow and NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations approached near-zero levels during the summer months. NO<sub>3</sub><sup>&#x2212;</sup>-N concentration levels were comparable at the collector drain and in the ditch during winter. Mean flow rates during the winter months (November until April) at the collector drain and in the ditch were 0.4 and 15.5&#x2009;L&#x2009;s<sup>&#x2212;1</sup>, respectively. Conversely, the collector drain often experienced dry conditions in summer (May until October), with an exception in the summer of 2011 when an extraordinary precipitation event (98&#x2009;mm day<sup>&#x2212;1</sup>) led to substantial flow. Mean flow rates in the ditch during summer were relatively low at 5.1&#x2009;L&#x2009;s<sup>&#x2212;1</sup>. Although NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations were typically below the drinking water limit of 11.3&#x2009;mg&#x2009;L<sup>&#x2212;1</sup> in summer (mean values of 8.0 and 3.1&#x2009;mg&#x2009;L<sup>&#x2212;1</sup> at the collector drain and in the ditch, respectively), they frequently exceeded this limit in winter (<xref ref-type="fig" rid="fig2">Figure 2</xref>) (mean values of 10.8 and 9.0&#x2009;mg&#x2009;L<sup>&#x2212;1</sup> at the collector drain and in the ditch, respectively).</p>
<fig position="float" id="fig2">
<label>Figure 2</label>
<caption>
<p>Daily flow rates (blue lines) and measured NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations (red dots) at the collector drain (above) and in the ditch (below) throughout the study period. NO<sub>3</sub><sup>&#x2212;</sup>-N measurements at the collector drain began on November 4, 2001, and measurements at the ditch, along with flow measurements at both stations, commenced on November 1, 2003. Data for this study were analyzed until April 30, 2023.</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g002.tif"/>
</fig>
<p>The general trend of low NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations in summer and high NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations in winter (<xref ref-type="fig" rid="fig2">Figure 2</xref>) can be attributed to the activation of different N sources. During the summer, characterized by low groundwater tables, it is reasonable to assume that mainly groundwater, with low NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations, contributes to the flow. In contrast, during winter when the water table rises, NO<sub>3</sub><sup>&#x2212;</sup>-rich water from the upper soil layers significantly influences the chemical composition of the discharge. This seasonal NO<sub>3</sub><sup>&#x2212;</sup>-N pattern in surface waters of agricultural catchments aligns with findings described by various researchers, including <xref ref-type="bibr" rid="ref43">Pionke et al. (1999)</xref>, <xref ref-type="bibr" rid="ref14">Dupas et al. (2016)</xref>, <xref ref-type="bibr" rid="ref20">Exner-Kittridge et al. (2016)</xref>, <xref ref-type="bibr" rid="ref22">Ford et al. (2018)</xref> and <xref ref-type="bibr" rid="ref1">Abbott et al. (2018)</xref>.</p>
<p>Over our observation period, no discernible trends were identified regarding the magnitude of NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations. The visual interpretation of <xref ref-type="fig" rid="fig2">Figure 2</xref> and the plotting of NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations as a function of flow (<xref ref-type="fig" rid="fig3">Figure 3</xref>) revealed a positive relationship between flow and NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations. This positive relationship between streamflow and NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations was more pronounced in the ditch (<xref ref-type="fig" rid="fig3">Figure 3</xref>). This can be attributed primarily to water flow from groundwater with very low NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations in the ditch during summer, whereas the discharge season at the collector drain is typically confined to the winter, during which NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations from drainage water are generally higher. The different NO<sub>3</sub><sup>&#x2212;</sup>-N concentration pattern of the collector drain and the ditch will be visible when plotting the NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations as histograms (<xref ref-type="fig" rid="fig4">Figure 4</xref>). The main difference between both figures is the large number of samples exhibit NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations from 0 to 5&#x2009;mg&#x2009;L<sup>&#x2212;1</sup> in the ditch. These samples were taken in the vast majority of cases in summer, when there was no water in the collector drain. Excluding these low concentration samples, both histograms are similar. Only, a small number of samples (104 at the drain collector and 44 in the ditch) contained NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations beyond 20&#x2009;mg&#x2009;L<sup>&#x2212;1</sup>.</p>
<fig position="float" id="fig3">
<label>Figure 3</label>
<caption>
<p>Relationships between NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations and flow rates at the collector drain (left) and the ditch (right).</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g003.tif"/>
</fig>
<fig position="float" id="fig4">
<label>Figure 4</label>
<caption>
<p>Histograms of NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations at the collector drain (left) and the ditch (right).</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g004.tif"/>
</fig>
<p>In summary, both flow patterns and the dynamic behavior of NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations at the collector drain and in the ditch exhibit a high temporal parallelism (<xref ref-type="fig" rid="fig2">Figure 2</xref>), emphasizing the significance of the artificial drainage system in discharge generation. Furthermore, it identifies the drainage system as a notable source of NO<sub>3</sub>-losses at larger spatial scales such as ditches, which confirms an earlier study conducted in the same study area analyzing a 3-years period of time (<xref ref-type="bibr" rid="ref47">Tiemeyer et al., 2006</xref>).</p>
</sec>
<sec id="sec9">
<label>3.2</label>
<title>Discharge and nitrate loads</title>
<p>NO<sub>3</sub><sup>&#x2212;</sup>-N loads (<xref rid="EQ1" ref-type="disp-formula">Equation 1</xref>) were clearly driven by discharge. This holds true both for a daily and for an annual evaluation (<xref ref-type="fig" rid="fig5">Figure 5</xref>). The relationship between flow and NO<sub>3</sub><sup>&#x2212;</sup>-N losses was even stronger compared to NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations. Annual NO<sub>3</sub><sup>&#x2212;</sup>-N loads varied greatly. Highest annual NO<sub>3</sub><sup>&#x2212;</sup>-N loads were observed at the collector drain (50&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>) and at the ditch (52&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>) in 2007 followed by very high loads in 2011, while NO<sub>3</sub><sup>&#x2212;</sup>-N loads were lowest in 2019. In that year, no NO<sub>3</sub><sup>&#x2212;</sup>-N was transported via the collector drain, since the collector drain did not carry any water and annual NO<sub>3</sub><sup>&#x2212;</sup>-N load was 1&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> at the ditch. These 2&#x2009;years reflect extreme weather conditions. The high NO<sub>3</sub><sup>&#x2212;</sup>-N loads in 2007 and 2011 were mainly caused by very wet conditions in summer, while the low NO<sub>3</sub><sup>&#x2212;</sup>-N loads in 2019 were a result of a prolonged drought period in 2018. Mean annual loads at the collector drain (19.7&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>) and the ditch (19.9&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>) were similar.</p>
<fig position="float" id="fig5">
<label>Figure 5</label>
<caption>
<p>Annual discharge and NO<sub>3</sub><sup>&#x2212;</sup>-N loads at the collector drain and the ditch and daily and annual relationships between these two parameters.</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g005.tif"/>
</fig>
<p>Due to the strong relationship between flow and NO<sub>3</sub><sup>&#x2212;</sup>-N loads it is not surprising that NO<sub>3</sub><sup>&#x2212;</sup>-N loads follow a pronounced seasonal pattern (<xref ref-type="fig" rid="fig6">Figure 6</xref>). High discharge rates in winter, in particular in January, February and March, caused high NO<sub>3</sub><sup>&#x2212;</sup>-N loads during that time. Consequently, highest monthly NO<sub>3</sub><sup>&#x2212;</sup>-N loads were recorded in January, both at the collector drain (4.7&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>) and at the ditch (4.4&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>), while NO<sub>3</sub><sup>&#x2212;</sup>-N loads were lowest in October at the collector drain (0.2&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>) and in September at the ditch (0.3&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup>).</p>
<fig position="float" id="fig6">
<label>Figure 6</label>
<caption>
<p>Mean monthly discharge and NO<sub>3</sub><sup>&#x2212;</sup>-N loads at the collector drain and the ditch. The vertical lines indicate standard deviations.</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g006.tif"/>
</fig>
<p>A significant amount of NO<sub>3</sub><sup>&#x2212;</sup>-N was leached during a short period of time and the majority of NO<sub>3</sub><sup>&#x2212;</sup>-N losses were restricted to winter. For example, the extraordinary high rainfall event (98&#x2009;mm) on July 23, 2011 led to 10% of the annual NO<sub>3</sub><sup>&#x2212;</sup>-N load being discharged within the next 7&#x2009;days. To underpin the importance of seasonality of NO<sub>3</sub><sup>&#x2212;</sup>-N leaching, it should be noted that 65 and 61% of the annual NO<sub>3</sub><sup>&#x2212;</sup>-N load is being between January and March at the collector drain and the ditch, respectively (<xref ref-type="fig" rid="fig6">Figure 6</xref>). These NO<sub>3</sub><sup>&#x2212;</sup>-N export mechanisms can be illustrated when the daily cumulative NO<sub>3</sub><sup>&#x2212;</sup>-N load starting with the highest load is plotted against time (<xref ref-type="fig" rid="fig7">Figure 7</xref>).</p>
<fig position="float" id="fig7">
<label>Figure 7</label>
<caption>
<p>Daily cumulative NO<sub>3</sub><sup>&#x2212;</sup>-N loads sorted starting with the highest load as a function of time.</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g007.tif"/>
</fig>
<p>When analyzing <xref ref-type="fig" rid="fig7">Figure 7</xref>, it is striking that the majority of the NO<sub>3</sub><sup>&#x2212;</sup>-N load is being discharged during a very short period of time. Twenty-seven days (out of 4,259 discharge days) with the highest NO<sub>3</sub><sup>&#x2212;</sup>-N loads were enough to contribute 10% of the total load at the collector drain. Even more extreme, 22&#x2009;days out of 6,679 discharge days contributed to 10% of NO<sub>3</sub><sup>&#x2212;</sup>-N load at the ditch. 50% of the total NO<sub>3</sub><sup>&#x2212;</sup>-N load was discharged, when 10 and 5% of the considered time period has passed at the collector drain and the ditch, respectively. At the other end of the spectrum, it can be stated that only 10% of the total NO<sub>3</sub><sup>&#x2212;</sup>-N load is being discharged in 50 and 75% of the total time at the collector drain and the ditch, respectively. The graph of the collector drain in <xref ref-type="fig" rid="fig7">Figure 7</xref> is flattened compared to the graph of the ditch. This is mainly because there is no flow and therefore no NO<sub>3</sub><sup>&#x2212;</sup>-N leaching at the collector drain in summer with very low NO<sub>3</sub><sup>&#x2212;</sup>-N loads. Generally, the range of the NO<sub>3</sub><sup>&#x2212;</sup>-N loads at the collector drain is smaller compared to the ditch due to missing low summer values.</p>
</sec>
<sec id="sec10">
<label>3.3</label>
<title>Nitrogen soil surface budget and nitrate export</title>
<p>From 2001 to 2022, The N input at the drainage plot ranged from 40&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup> to 275&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup>, while the N input varied from 109&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup> to 228&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup> in the ditch catchment. N output ranged from 26 to 232&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup> and from 99 to 163&#x2009;kg&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup> for the drainage plot and the ditch catchment, respectively. These values align with typical conventional farming practices in northeastern Germany. N soil surface budgets (<xref rid="EQ2" ref-type="disp-formula">Equation 2</xref>) in our study area mostly exhibited positive values due to higher input than export through harvest (<xref ref-type="fig" rid="fig8">Figure 8</xref> and <xref ref-type="table" rid="tab1">Table 1</xref>). Notably, the ditch catchment exhibited less variability in N input, output, and soil surface budgets, benefiting from the inclusion of four fields with different cultivation practices instead of one single field (drainage plot). When the cumulative N soil surface budgets and NO<sub>3</sub><sup>&#x2212;</sup>-N losses via the collector drain and the ditch over the course of the study period are subtracted, a surplus of 295&#x2009;kg&#x2009;N (drainage plot) and 268&#x2009;kg&#x2009;N (ditch catchment) is evident. This suggests a long-term accumulation of N in the soils despite the fact that, based on the prevailing soil types and impact of groundwater, ca. 10&#x2013;30&#x2009;kg&#x2009;N&#x2009;ha<sup>&#x2212;1</sup> year<sup>&#x2212;1</sup> may have been lost through denitrification (<xref ref-type="bibr" rid="ref28">Kreins et al., 2010</xref>). NO<sub>3</sub><sup>&#x2212;</sup>-rich soil water is potentially available for leaching and becomes active when the groundwater table rises. This probably explains the observed seasonal patterns of NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations and the positive relationships between flow and NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations in our study catchment. The significance of groundwater head in nitrate export has been highlighted in previous studies (<xref ref-type="bibr" rid="ref38">Musolff et al., 2016</xref>).</p>
<fig position="float" id="fig8">
<label>Figure 8</label>
<caption>
<p>N input, N output, N soil surface budget (N<sub>sur</sub>) and NO<sub>3</sub><sup>&#x2212;</sup>-N loads for the drainage plot (above) and the ditch catchment (below) and annual precipitation.</p>
</caption>
<graphic xlink:href="frwa-06-1369552-g008.tif"/>
</fig>
<p>NO<sub>3</sub><sup>&#x2212;</sup>-N loads were completely independent from the N management on the arable fields and highest loads were observed during the wettest years 2007 and 2011 (<xref ref-type="fig" rid="fig8">Figure 8</xref>). In contrast to findings in other studies (<xref ref-type="bibr" rid="ref29">Larsson and Jarvis, 1999</xref>; <xref ref-type="bibr" rid="ref22">Ford et al., 2018</xref>; <xref ref-type="bibr" rid="ref30">Liu et al., 2022</xref>), our results confirm earlier studies of our working group, in which no direct relationships between the N soil surface budget and N export (<xref ref-type="bibr" rid="ref6">Bauwe et al., 2020</xref>) was identified. Contrarily, NO<sub>3</sub>-export in our study catchment and also in other catchments of the Baltic Sea Region (<xref ref-type="bibr" rid="ref8">Bechmann et al., 2014</xref>) appear to be entirely independent of N fertilizer application rates and is solely driven by hydro-meteorological factors.</p>
</sec>
<sec id="sec11">
<label>3.4</label>
<title>Implications for catchment management</title>
<p>The data analysis in this study had two significant findings. Firstly, the previously described seasonal fluctuations in NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations and discharge had profound implications for NO<sub>3</sub>-export. Considering the entire time frame, the majority of NO<sub>3</sub><sup>&#x2212;</sup>-N has been lost via the collector drain or the ditch during a very short period (<xref ref-type="fig" rid="fig7">Figure 7</xref>). Secondly, no direct relationships between N soil surface budget and NO<sub>3</sub>-export were discerned at either the drainage plot or the ditch (<xref ref-type="fig" rid="fig8">Figure 8</xref>). Although the N soil surface budget generally exhibited a decreasing trend, this reduction did not correlate with changes in NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations (<xref ref-type="fig" rid="fig2">Figure 2</xref>).</p>
<p>These findings have implications for a catchment management aiming at mitigating NO<sub>3</sub><sup>&#x2212;</sup>-N losses. Efforts should be intensified to further reduce the N surplus. While there is an overarching trend in Germany and other European countries toward gradually decreasing agricultural N surplus (<xref ref-type="bibr" rid="ref4">Batool et al., 2022</xref>), it is important to recognize that the positive impact on riverine NO<sub>3</sub>-export may take many years to materialize. The predominant reason for this prolonged delay, known as the &#x201C;N legacy effect,&#x201D; refers to the enduring accumulation of N in the root zone (<xref ref-type="bibr" rid="ref50">Van Meter et al., 2016</xref>). The long-term N accumulation in the upper soil layers might also explain, why there are no functional seasonal relationships between agricultural activities such as N fertilization and NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations in our study area. In contrast, there are instances, in which NO<sub>3</sub><sup>&#x2212;</sup>-transport in the river was affected by seasonal changes of the N soil system budgets (<xref ref-type="bibr" rid="ref42">Pinardi et al., 2022</xref>). Under climate change conditions, both NO<sub>3</sub><sup>&#x2212;</sup>-N export mechanisms and biogeochemical cycles may change, which makes predictions regarding NO<sub>3</sub><sup>&#x2212;</sup>-N losses difficult. On the one hand, expected wetter winters in Central Europe (<xref ref-type="bibr" rid="ref23">Frei et al., 2006</xref>) will probably lead to increased NO<sub>3</sub><sup>&#x2212;</sup>-N loads because of elevated discharge in winter. On the other hand, rising temperatures will presumably result in higher denitrification rates (<xref ref-type="bibr" rid="ref13">de Klein et al., 2017</xref>), which will might have a positive effect on NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations and loads in surface waters. For example, a downward trend in N export during the last three decades was observed for the Po River in Italy, and it was associated with an upward trend in water temperature along with enhanced denitrification rates (<xref ref-type="bibr" rid="ref46">Soana et al., 2024</xref>).</p>
<p>To expedite the transition to a sustainable N management in agricultural catchments, technical measures should be implemented. Given that artificial drainage systems exert significant control over the hydrology and hydrochemistry of larger scales (<xref ref-type="bibr" rid="ref47">Tiemeyer et al., 2006</xref>), reduction measures should primarily target drainage plot outlets. Effective strategies may include the establishment of constructed wetlands (<xref ref-type="bibr" rid="ref27">Kovacic et al., 2000</xref>; <xref ref-type="bibr" rid="ref12">Crumpton et al., 2020</xref>; <xref ref-type="bibr" rid="ref33">Mitchell et al., 2023</xref>) or the implementation of reactive barriers (<xref ref-type="bibr" rid="ref10">Christianson et al., 2012</xref>, <xref ref-type="bibr" rid="ref11">2021</xref>; <xref ref-type="bibr" rid="ref33">Mitchell et al., 2023</xref>). Both approaches also have the potential to mitigate high flows, thereby positively influencing NO<sub>3</sub><sup>&#x2212;</sup>-N concentrations during discharge events. However, in the scientific literature it is also argued that conservation practices (less fertilization, crop rotation etc.) possibly lead to faster success than controlled drainage, bioreactors, or saturated buffers (<xref ref-type="bibr" rid="ref30">Liu et al., 2022</xref>).</p>
<p>Because of remaining uncertainties, probably the best approach for a sustainable N management in agricultural catchments is the implementation and strengthening of conservation practices together with technical solutions in hot spot areas.</p>
</sec>
</sec>
<sec sec-type="conclusions" id="sec12">
<label>4</label>
<title>Conclusion</title>
<p>In conclusion, our two-decade-long intensive monitoring of hydrology and NO<sub>3</sub>-export in a nested tile-drained agricultural catchment has provided insights into the complex dynamics of N losses from agricultural land. The main findings of this investigation can be summarized as follows:</p>
<list list-type="simple">
<list-item><p>(1) Seasonal NO<sub>3</sub>-export: the study revealed distinct seasonal patterns in NO<sub>3</sub><sup>&#x2212;</sup> concentrations and export, with elevated levels during winter months. NO<sub>3</sub>-export dynamics were closely linked to hydro-meteorological conditions, which underlines the significant influence of weather and hydrologic factors on NO<sub>3</sub>-losses. The majority of the annual NO<sub>3</sub><sup>&#x2212;</sup> load was transported within a few days, highlighting the episodic nature of NO<sub>3</sub>-export in the catchment.</p></list-item>
<list-item><p>(2) Limited influence of N soil Surface budgets: surprisingly, no direct relationships were found between N soil surface budgets and NO<sub>3</sub>-losses. The temporal dynamics of NO<sub>3</sub>-export were primarily determined by hydro-meteorological conditions.</p></list-item>
<list-item><p>(3) Implications for catchment management: the findings underscore the challenges in mitigating NO<sub>3</sub>-losses from agricultural land, suggesting that reductions in N surplus may take years to have a positive effect on NO<sub>3</sub><sup>&#x2212;</sup> concentrations due to the &#x201C;N legacy effect.&#x201D; Effective catchment management strategies should consider the impact of artificial drainage systems on NO<sub>3</sub>-export and focus on hot spot areas, possibly through the implementation of technical measures such as constructed wetlands or reactive barriers, in conjunction with conservation practices.</p></list-item>
</list>
</sec>
<sec sec-type="data-availability" id="sec13">
<title>Data availability statement</title>
<p>The raw data supporting the conclusions of this article will be made available by the authors, without undue reservation.</p>
</sec>
<sec sec-type="author-contributions" id="sec14">
<title>Author contributions</title>
<p>AB: Conceptualization, Formal analysis, Methodology, Writing &#x2013; original draft. BL: Conceptualization, Supervision, Writing &#x2013; review &#x0026; editing.</p>
</sec>
</body>
<back>
<sec sec-type="funding-information" id="sec15">
<title>Funding</title>
<p>The author(s) declare that no financial support was received for the research, authorship, and/or publication of this article.</p>
</sec>
<ack>
<p>The authors would like to thank Marianne Kietzmann and Evelyn Bolzmann for the extensive chemical analyses and Tilo Hartwig for his assistance with the fieldwork.</p>
</ack>
<sec sec-type="COI-statement" id="sec16">
<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 id="sec100" sec-type="disclaimer">
<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 claim that may be made by its manufacturer, is not guaranteed or endorsed by the publisher.</p>
</sec>
<fn-group>
<fn id="fn0001">
<p><sup>1</sup><ext-link xlink:href="https://gis.uba.de/website/depo1/" ext-link-type="uri">https://gis.uba.de/website/depo1/</ext-link>
</p>
</fn>
</fn-group>
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