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  <front>
    <journal-meta><journal-id journal-id-type="publisher">HESS</journal-id><journal-title-group>
    <journal-title>Hydrology and Earth System Sciences</journal-title>
    <abbrev-journal-title abbrev-type="publisher">HESS</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Hydrol. Earth Syst. Sci.</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1607-7938</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/hess-27-2989-2023</article-id><title-group><article-title>Uncertainty in water transit time estimation with StorAge Selection functions and tracer data interpolation</article-title><alt-title>Uncertainty in water transit time estimation with SAS functions</alt-title>
      </title-group><?xmltex \runningtitle{Uncertainty in water transit time estimation with SAS functions}?><?xmltex \runningauthor{A. Borriero et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Borriero</surname><given-names>Arianna</given-names></name>
          <email>arianna.borriero@ufz.de</email>
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Kumar</surname><given-names>Rohini</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-4396-2037</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Nguyen</surname><given-names>Tam V.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff3">
          <name><surname>Fleckenstein</surname><given-names>Jan H.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-7213-9448</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Lutz</surname><given-names>Stefanie R.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-9583-7337</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Department of Hydrogeology, Helmholtz Centre for Environmental Research – UFZ, Leipzig, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Department of Computational Hydrosystems, Helmholtz Centre for Environmental Research – UFZ, Leipzig, Germany</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Bayreuth Centre of Ecology and Environmental Research, University of Bayreuth, Bayreuth, Germany</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>Copernicus Institute of Sustainable Development, Department of Environmental Sciences, <?xmltex \hack{\break}?>Utrecht University, Utrecht, the Netherlands</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Arianna Borriero (arianna.borriero@ufz.de)</corresp></author-notes><pub-date><day>14</day><month>August</month><year>2023</year></pub-date>
      
      <volume>27</volume>
      <issue>15</issue>
      <fpage>2989</fpage><lpage>3004</lpage>
      <history>
        <date date-type="received"><day>10</day><month>June</month><year>2022</year></date>
           <date date-type="rev-request"><day>26</day><month>July</month><year>2022</year></date>
           <date date-type="rev-recd"><day>22</day><month>June</month><year>2023</year></date>
           <date date-type="accepted"><day>2</day><month>July</month><year>2023</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2023 Arianna Borriero et al.</copyright-statement>
        <copyright-year>2023</copyright-year>
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023.html">This article is available from https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023.html</self-uri><self-uri xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023.pdf">The full text article is available as a PDF file from https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023.pdf</self-uri>
      <abstract><title>Abstract</title>

      <p id="d1e140">Transit time distributions (TTDs) of streamflow are useful descriptors for understanding flow and solute transport in catchments. Catchment-scale TTDs can be modeled using tracer data (e.g. oxygen isotopes, such as <inline-formula><mml:math id="M1" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>) in inflow and outflows by employing StorAge Selection (SAS) functions.
However, tracer data are often sparse in space and time, so they need to be interpolated to increase their spatiotemporal resolution. Moreover, SAS functions can be parameterized with different forms, but there is no general agreement on which one should be used. Both of these aspects induce uncertainty in the simulated TTDs, and the individual uncertainty sources as well as their combined effect have not been fully investigated.
This study provides a comprehensive analysis of the TTD uncertainty resulting from 12 model setups obtained by combining different interpolation schemes for <inline-formula><mml:math id="M2" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in precipitation and distinct SAS functions.
For each model setup, we found behavioral solutions with satisfactory model performance for in-stream  <inline-formula><mml:math id="M3" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> (KGE <inline-formula><mml:math id="M4" display="inline"><mml:mo>&gt;</mml:mo></mml:math></inline-formula> 0.55, where KGE refers to the Kling–Gupta efficiency). Differences in KGE values were statistically significant, thereby showing the relevance of the chosen setup for simulating TTDs.
We found a large uncertainty in the simulated TTDs, represented by a large range of variability in the 95 % confidence interval of the median transit time, varying at the most by between 259 and 1009 d across all tested setups. Uncertainty in TTDs was mainly associated with the temporal interpolation of <inline-formula><mml:math id="M5" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in precipitation, the choice between time-variant and time-invariant SAS functions, flow conditions, and the use of nonspatially interpolated <inline-formula><mml:math id="M6" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in precipitation.
We discuss the implications of these results for the SAS framework, uncertainty characterization in TTD-based models, and the influence of the uncertainty for water quality and quantity studies.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <?pagebreak page2990?><p id="d1e225">Understanding how catchments store and release water of different ages has significant implications for flow and solute transport, as water ages encapsulate information about flow paths' characteristics <xref ref-type="bibr" rid="bib1.bibx67 bib1.bibx22" id="paren.1"/>, the contact time of solutes with the soil matrix <xref ref-type="bibr" rid="bib1.bibx10 bib1.bibx42" id="paren.2"/>, and vulnerability assessment <xref ref-type="bibr" rid="bib1.bibx59" id="paren.3"/>. This plays an important role in water resources protection and management, and it requires a tool that can effectively describe catchment-scale transport processes <xref ref-type="bibr" rid="bib1.bibx75" id="paren.4"/>. The age of water in outflows is commonly referred to as transit time (TT), i.e. the time that elapses between the entry of a water parcel into the catchment via precipitation and its exit via streamflow or evapotranspiration. Accordingly, the transit time distribution (TTD) describes the whole spectrum of transit times in outflows <xref ref-type="bibr" rid="bib1.bibx20 bib1.bibx92" id="paren.5"/>. Early studies have often assumed simplified steady-state transport models, resulting in time-invariant TTDs <xref ref-type="bibr" rid="bib1.bibx72 bib1.bibx76" id="paren.6"/>. However, experimental simulations have shown that TTDs are time-variant due to the variability in meteorological forcing <xref ref-type="bibr" rid="bib1.bibx21 bib1.bibx39 bib1.bibx37" id="paren.7"/> and the activation/deactivation of flow paths in response to varying hydrologic conditions <xref ref-type="bibr" rid="bib1.bibx4 bib1.bibx36" id="paren.8"/>.
Recent research has introduced new models for representing time-variant TTDs, for example, allowing for the estimation of TTDs without making prior assumptions about their shape <xref ref-type="bibr" rid="bib1.bibx52 bib1.bibx48" id="paren.9"/> or with the parameterization of the StorAge Selection (SAS) functions <xref ref-type="bibr" rid="bib1.bibx77 bib1.bibx35" id="paren.10"/>. SAS functions describe how catchments selectively remove water of different ages from storage for outflows, and they have led to a new framework of nonstationary transport models based on water age, which have been successfully applied in various studies <xref ref-type="bibr" rid="bib1.bibx11 bib1.bibx74 bib1.bibx49 bib1.bibx63 bib1.bibx101 bib1.bibx70" id="paren.11"/>.</p>
      <p id="d1e262">Model-based TTDs are subjected to uncertainty, which limits their ability with respect to decision support. In general, model prediction uncertainty stems from model inputs, structure, and parameters <xref ref-type="bibr" rid="bib1.bibx15" id="paren.12"/>.
As TTDs are not directly observable, conservative environmental tracers (e.g. oxygen isotopes, such as <inline-formula><mml:math id="M7" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>) in inflow and outflows are commonly used to infer water ages <xref ref-type="bibr" rid="bib1.bibx41 bib1.bibx16 bib1.bibx87" id="paren.13"/>. Long-term, high-frequency tracer data with an appropriate spatial distribution are generally recommended for a sufficient understanding of TTD dynamics across a wide range of fast and heterogeneous hydrological behaviors <xref ref-type="bibr" rid="bib1.bibx55 bib1.bibx25 bib1.bibx97" id="paren.14"/>. Therefore, a lack of appropriate tracer data coverage can hamper our understanding of TTD dynamics at the desired resolution <xref ref-type="bibr" rid="bib1.bibx67" id="paren.15"/>. Additionally, uncertainty in the driving hydroclimatic fluxes, such as precipitation, discharge, and evapotranspiration, could propagate into the uncertainty in the modeling results.
Further uncertainty emerges from the model structure due to the difficulty in representing physical processes because of our incomplete knowledge of complex reality <xref ref-type="bibr" rid="bib1.bibx2" id="paren.16"/>. Finally, specification of model parameters is also an important source of uncertainty <xref ref-type="bibr" rid="bib1.bibx14 bib1.bibx50" id="paren.17"/>, as the best-fit parameters may suffer from equifinality <xref ref-type="bibr" rid="bib1.bibx82" id="paren.18"/>.</p>
      <p id="d1e300">A few studies have investigated the uncertainty in the estimated TTDs with SAS models. <xref ref-type="bibr" rid="bib1.bibx26" id="text.19"/> and <xref ref-type="bibr" rid="bib1.bibx47" id="text.20"/> analyzed the effect of interactions between distinct flow domains, external forcing, and recharge rate on the resulting TTDs. Several works <xref ref-type="bibr" rid="bib1.bibx12 bib1.bibx101 bib1.bibx78 bib1.bibx79" id="paren.21"/> have explored model parameter uncertainty and suggested that additional types of tracers, data on physical characteristics of the catchment, and parsimonious parameterization may help to further reduce parametric uncertainty in the SAS models. More recently, <xref ref-type="bibr" rid="bib1.bibx23" id="text.22"/> investigated how gap-filling of the <inline-formula><mml:math id="M8" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> record in precipitation propagated uncertainty into the simulated mean water transit time (MTT), i.e. the average time it takes for water to leave the catchment <xref ref-type="bibr" rid="bib1.bibx66" id="paren.23"/>.</p>
      <p id="d1e332">Despite the studies cited above, there are other aspects that are particularly significant for SAS modeling and cause uncertainty in the simulated TTDs that have not yet been thoroughly investigated.
First, isotope data are generally sparse globally in space and time <xref ref-type="bibr" rid="bib1.bibx99" id="paren.24"/>, due to laborious and costly sampling campaigns limited to well-equipped areas <xref ref-type="bibr" rid="bib1.bibx90" id="paren.25"/>. As SAS models require continuous time series of input tracer data, different methods for temporal interpolation could be used to reconstruct isotope values in precipitation; consequently, the interpolated input data are subject to uncertainty.
Furthermore, the input data of SAS models are influenced by whether the tracer data in precipitation are collected at a single location within the catchment or at multiple locations. In the latter scenario, there is a need to account for the spatial variability in the tracer composition in precipitation, which is commonly done via spatial interpolation. Choosing data from one approach (i.e. tracer data from a single location) over the other (i.e. tracer data spatially interpolated based on multiple locations, including stations outside the catchment boundaries) can potentially result in different resulting TTDs.
Finally, SAS functions, employed to model TTDs, must be parameterized, and their functional forms need to be specified a priori. Commonly used forms are the power law <xref ref-type="bibr" rid="bib1.bibx12 bib1.bibx6" id="paren.26"/>, beta <xref ref-type="bibr" rid="bib1.bibx93 bib1.bibx27" id="paren.27"/>, and gamma <xref ref-type="bibr" rid="bib1.bibx34 bib1.bibx101" id="paren.28"/> distributions. However, there is no general agreement on which SAS function should be used, as the hydrological processes that control the patterns and dynamics of the subsurface vary across catchments. Therefore, the most convenient approach is to simply rely on a specific parameterization over another and estimate its parameters <xref ref-type="bibr" rid="bib1.bibx34" id="paren.29"/>. All of these aspects, related to model input, structure, and parameters, induce uncertainty in the simulated TTDs. To date, the role of these individual uncertainty sources and their combined effect on the modeled TTDs have not been adequately discussed.</p>
      <p id="d1e355">This study bridges the aforementioned gaps by specifically exploring the combined effect of tracer data interpolation and model parameterizations on the simulated TTDs.
We investigated TTD uncertainty using an SAS-based catchment-scale transport model applied to the upper Selke catchment, Germany. We evaluated TTDs resulting from 12 model setups obtained by combining distinct interpolation techniques of <inline-formula><mml:math id="M9" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in precipitation and parameterizations of SAS functions. For each model setup, we searched for behavioral parameter sets (i.e. those providing acceptable predictions) based on model performance for in-stream <inline-formula><mml:math id="M10" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and we evaluated the sources of uncertainty and their combined effects in the modeled TTDs. Overall, our results provide new insights into the uncertainty characterization of TTDs, particularly in the absence of high-frequency tracer data, and the<?pagebreak page2991?> use of SAS functions as well as the implications of TTDs' uncertainty on water quantity and quality studies.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Study area and data</title>
      <p id="d1e392">The upper Selke catchment is located in the Harz Mountains in Saxony-Anhalt, central Germany (Fig. <xref ref-type="fig" rid="Ch1.F1"/>). The study site is part of the Bode region, an intensively monitored area within the TERENO <xref ref-type="bibr" rid="bib1.bibx104" id="paren.30"><named-content content-type="pre">TERrestrial ENvironmental Observatories;</named-content></xref> network. The catchment has a drainage area of 184 km<inline-formula><mml:math id="M11" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula>, the altitude ranges between 184 and
594 m above mean sea level, and the mean slope is 7.65 %. Land use is dominated by forest (broadleaf, coniferous, and mixed forest) and agricultural land (winter cereals, rapeseed, and maize), representing 72 % and 21 % of the catchment, respectively. The soil is largely composed of Cambisols and the underlying geology consists of schist and claystone, resulting in a predominance of relatively shallow flow paths <xref ref-type="bibr" rid="bib1.bibx30 bib1.bibx106" id="paren.31"/>.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1"><?xmltex \currentcnt{1}?><?xmltex \def\figurename{Figure}?><label>Figure 1</label><caption><p id="d1e416">The upper Selke catchment, showing precipitation sampling points (purple dots), the river network (blue lines), and the elevation (in meters above sea level) as a colored map. The inset presents the location of the upper Selke catchment in Germany.</p></caption>
        <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023-f01.png"/>

      </fig>

      <p id="d1e425">Daily hydroclimatic and monthly tracer data in the upper Selke catchment were available for the period between February 2013 and May 2015. Precipitation (<inline-formula><mml:math id="M12" display="inline"><mml:mi>P</mml:mi></mml:math></inline-formula>) was taken from the German Weather Service, whereas discharge (<inline-formula><mml:math id="M13" display="inline"><mml:mi>Q</mml:mi></mml:math></inline-formula>) and evapotranspiration (ET) were simulated data obtained from the mesoscale Hydrological Model <xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx58" id="paren.32"><named-content content-type="pre">mHM;</named-content></xref>, as continuous measurements were not available for the given outlet and period. A thorough evaluation of mHM performance for past measurements has been conducted in previous studies <xref ref-type="bibr" rid="bib1.bibx108 bib1.bibx107 bib1.bibx70" id="paren.33"/>. The average annual <inline-formula><mml:math id="M14" display="inline"><mml:mi>P</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math id="M15" display="inline"><mml:mi>Q</mml:mi></mml:math></inline-formula>, and ET are 703, 108, and 596 mm, respectively. The area is characterized by high flow during November–May (average <inline-formula><mml:math id="M16" display="inline"><mml:mrow><mml:mi>Q</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.88</mml:mn></mml:mrow></mml:math></inline-formula> m <inline-formula><mml:math id="M17" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> s<inline-formula><mml:math id="M18" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>) and low flow during June–October (average <inline-formula><mml:math id="M19" display="inline"><mml:mrow><mml:mi>Q</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.42</mml:mn></mml:mrow></mml:math></inline-formula> m <inline-formula><mml:math id="M20" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> s<inline-formula><mml:math id="M21" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>). Evapotranspiration is higher in June (109 mm per month) and lower in December (10 mm per month). The average monthly temperature ranges from <inline-formula><mml:math id="M22" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.7</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M23" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in January to 17 <inline-formula><mml:math id="M24" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in July.
The <inline-formula><mml:math id="M25" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values in precipitation (<inline-formula><mml:math id="M26" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) and in streamflow (<inline-formula><mml:math id="M27" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) at a monthly resolution were taken from <xref ref-type="bibr" rid="bib1.bibx64" id="text.34"/> and are displayed in Fig. <xref ref-type="fig" rid="Ch1.F2"/>. Values of <inline-formula><mml:math id="M28" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> were used in the form of “raw” (i.e. values collected at the catchment outlet) and “processed” (i.e. values collected at multiple locations and spatially interpolated using kriging) data (see Sect. <xref ref-type="sec" rid="Ch1.S3.SS2"/> for more details). The variability in <inline-formula><mml:math id="M29" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> was larger than that in <inline-formula><mml:math id="M30" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F2"/>) because of the damping of the precipitation signal due to mixing and dispersion within the catchment. Temperature dependence caused more depleted (i.e. more negative) <inline-formula><mml:math id="M31" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in winter than in summer (Fig. <xref ref-type="fig" rid="Ch1.F2"/>).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><?xmltex \currentcnt{2}?><?xmltex \def\figurename{Figure}?><label>Figure 2</label><caption><p id="d1e685">Data of <inline-formula><mml:math id="M32" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in precipitation (kriged values as pink dots and raw values as yellow dots) and streamflow (blue dots).</p></caption>
        <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023-f02.png"/>

      </fig>

</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Methods</title>
<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>Catchment-scale transport model</title>
      <p id="d1e722">In this study, we used the <italic>tran</italic>-SAS model <xref ref-type="bibr" rid="bib1.bibx7" id="paren.35"/> for describing the catchment-scale water mixing and solute transport based on SAS functions. The catchment was conceptualized as a single storage <inline-formula><mml:math id="M33" display="inline"><mml:mrow><mml:mi>S</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (mm), whose water-age balance can be expressed as follows <xref ref-type="bibr" rid="bib1.bibx7" id="paren.36"/>:

                <disp-formula specific-use="gather" content-type="numbered"><mml:math id="M34" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E1"><mml:mtd><mml:mtext>1</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi>S</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:mi>V</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E2"><mml:mtd><mml:mtext>2</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mtable class="split" rowspacing="0.2ex" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd><mml:mrow><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>∂</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mo>∂</mml:mo><mml:mi>t</mml:mi></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mo>+</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>∂</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mo>∂</mml:mo><mml:mi>T</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>=</mml:mo><mml:mi>P</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>-</mml:mo><mml:mi>Q</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:msub><mml:mi mathvariant="normal">Ω</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mo>-</mml:mo><mml:mi mathvariant="normal">ET</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:msub><mml:mi mathvariant="normal">Ω</mml:mi><mml:mi mathvariant="normal">ET</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E3"><mml:mtd><mml:mtext>3</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mtext>with an initial condition of </mml:mtext><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E4"><mml:mtd><mml:mtext>4</mml:mtext></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mtext>and a boundary condition of </mml:mtext><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

            Here, <inline-formula><mml:math id="M35" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (mm) is the initial storage; <inline-formula><mml:math id="M36" display="inline"><mml:mrow><mml:mi>V</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (mm) represents the storage variations; <inline-formula><mml:math id="M37" display="inline"><mml:mrow><mml:mi>P</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (mm d<inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), <inline-formula><mml:math id="M39" display="inline"><mml:mrow><mml:mi>Q</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (mm d<inline-formula><mml:math id="M40" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), and ET<inline-formula><mml:math id="M41" display="inline"><mml:mrow><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (mm d<inline-formula><mml:math id="M42" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>) are precipitation, discharge, and evapotranspiration, respectively; <inline-formula><mml:math id="M43" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (mm) is the age-ranked storage;  <inline-formula><mml:math id="M44" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (mm) is the initial age-ranked storage; and <inline-formula><mml:math id="M45" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Ω</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (–) and <inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">Ω</mml:mi><mml:mi mathvariant="normal">ET</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (–) are the cumulative SAS functions for <inline-formula><mml:math id="M47" display="inline"><mml:mi>Q</mml:mi></mml:math></inline-formula> and ET, respectively.</p>
      <?pagebreak page2992?><p id="d1e1207">By definition, the TTD of streamflow <inline-formula><mml:math id="M48" display="inline"><mml:mrow><mml:msub><mml:mi>p</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (d<inline-formula><mml:math id="M49" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>) is calculated as follows <xref ref-type="bibr" rid="bib1.bibx7" id="paren.37"/>:
            <disp-formula id="Ch1.E5" content-type="numbered"><label>5</label><mml:math id="M50" display="block"><mml:mrow><mml:msub><mml:mi>p</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>∂</mml:mo><mml:msub><mml:mi mathvariant="normal">Ω</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mo>∂</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>⋅</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>∂</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi>T</mml:mi></mml:msub></mml:mrow><mml:mrow><mml:mo>∂</mml:mo><mml:mi>T</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e1318">The isotopic signature in streamflow <inline-formula><mml:math id="M51" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (‰) can be obtained as follows <xref ref-type="bibr" rid="bib1.bibx7" id="paren.38"/>:
            <disp-formula id="Ch1.E6" content-type="numbered"><label>6</label><mml:math id="M52" display="block"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:munderover><mml:mo movablelimits="false">∫</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mrow><mml:mo>+</mml:mo><mml:mi mathvariant="normal">∞</mml:mi></mml:mrow></mml:munderover><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:msub><mml:mi>p</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">d</mml:mi><mml:mi>T</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where <inline-formula><mml:math id="M53" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (‰) is the isotopic signature of a water parcel in storage. Equations (<xref ref-type="disp-formula" rid="Ch1.E5"/>) and (<xref ref-type="disp-formula" rid="Ch1.E6"/>) also apply for ET.</p>
      <p id="d1e1438">In this study, we tested three SAS parameterizations: the power law time-invariant (PLTI; Eq. <xref ref-type="disp-formula" rid="Ch1.E7"/>, <xref ref-type="bibr" rid="bib1.bibx74" id="altparen.39"/>), power law time-variant (PLTV; Eq. <xref ref-type="disp-formula" rid="Ch1.E8"/>,  <xref ref-type="bibr" rid="bib1.bibx12" id="altparen.40"/>), and beta time-invariant  (BETATI; Eq. <xref ref-type="disp-formula" rid="Ch1.E9"/>, <xref ref-type="bibr" rid="bib1.bibx27" id="altparen.41"/>) distributions. Here, they are expressed as probability density functions in terms of the normalized age-ranked storage <inline-formula><mml:math id="M54" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (–), also known as fractional SAS functions (fSAS):

                <disp-formula specific-use="align" content-type="numbered"><mml:math id="M55" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E7"><mml:mtd><mml:mtext>7</mml:mtext></mml:mtd><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mi mathvariant="italic">ω</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>k</mml:mi><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mi>k</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E8"><mml:mtd><mml:mtext>8</mml:mtext></mml:mtd><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mi mathvariant="italic">ω</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>k</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mi>k</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E9"><mml:mtd><mml:mtext>9</mml:mtext></mml:mtd><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi mathvariant="italic">ω</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">S</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>T</mml:mi><mml:mo>,</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mi mathvariant="italic">β</mml:mi><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow><mml:mrow><mml:mi>B</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="italic">α</mml:mi><mml:mo>,</mml:mo><mml:mi mathvariant="italic">β</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula></p>
      <p id="d1e1754">The parameters <inline-formula><mml:math id="M56" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math id="M57" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>, and <inline-formula><mml:math id="M58" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula> determine the catchment's water-age preference for outflows, while <inline-formula><mml:math id="M59" display="inline"><mml:mrow><mml:mi>B</mml:mi><mml:mo>(</mml:mo><mml:mi mathvariant="italic">α</mml:mi><mml:mo>,</mml:mo><mml:mi mathvariant="italic">β</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is the two-parameter beta function. If <inline-formula><mml:math id="M60" display="inline"><mml:mrow><mml:mi>k</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, or if <inline-formula><mml:math id="M61" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M62" display="inline"><mml:mrow><mml:mi mathvariant="italic">β</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, the system tends to discharge young water. If <inline-formula><mml:math id="M63" display="inline"><mml:mrow><mml:mi>k</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, or if <inline-formula><mml:math id="M64" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M65" display="inline"><mml:mrow><mml:mi mathvariant="italic">β</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, the catchment preferably releases old water. The case of <inline-formula><mml:math id="M66" display="inline"><mml:mrow><mml:mi>k</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> or <inline-formula><mml:math id="M67" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo><mml:mi mathvariant="italic">β</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> describes no selection preference (i.e. complete water mixing). PLTV is characterized by <inline-formula><mml:math id="M68" display="inline"><mml:mrow><mml:mi>k</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> varying linearly over time between two extremes, <inline-formula><mml:math id="M69" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M70" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, as a function of the catchment wetness wi (–), i.e. <inline-formula><mml:math id="M71" display="inline"><mml:mrow><mml:mi mathvariant="normal">wi</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:mi>S</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>-</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">min</mml:mi></mml:msub><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">max</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">min</mml:mi></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, where  <inline-formula><mml:math id="M72" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">min</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M73" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">max</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are the respective minimum and maximum storage values over the entire period.</p>
</sec>
<sec id="Ch1.S3.SS2">
  <label>3.2</label><?xmltex \opttitle{Interpolation techniques for ${\protect\chem{\delta^{{18}}O}}$ in precipitation}?><title>Interpolation techniques for <inline-formula><mml:math id="M74" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in precipitation</title>
      <p id="d1e2033">We tested the model with two spatial representation and two temporal interpolation methods for <inline-formula><mml:math id="M75" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> to explore the impact of input tracer data on model performance, results, and uncertainty.
To evaluate the effect of spatial representation, we firstly used single-point <inline-formula><mml:math id="M76" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> measurements, which we refer to in the following as raw <inline-formula><mml:math id="M77" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. These measurements, obtained from <xref ref-type="bibr" rid="bib1.bibx64" id="text.42"/>, were taken at the catchment outlet.
The selection of <inline-formula><mml:math id="M78" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> at the outlet assumes a precipitation collector close to the stream gauge at the outlet, which is a common occurrence in many catchments for logistical reasons. Indeed, the outlet, where in-stream <inline-formula><mml:math id="M79" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> is sampled, serves as the location where all precipitation inputs across the catchment are integrated. For convenience, precipitation monitoring is also often conducted at or near the gauging station at the outlet.
Secondly, we used spatially interpolated <inline-formula><mml:math id="M80" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> with kriging based on multiple locations. The spatial interpolation was conducted in <xref ref-type="bibr" rid="bib1.bibx64" id="text.43"/> using raw <inline-formula><mml:math id="M81" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> from 24 precipitation collectors spread over the larger Bode region and using altitude as external drift. In a further step, the kriged <inline-formula><mml:math id="M82" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> data were weighted with spatially distributed monthly precipitation to obtain representative estimates for the study catchment. In our study, the kriged <inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> resulted in slightly more negative values than the raw <inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> from the catchment outlet (Fig. <xref ref-type="fig" rid="Ch1.F2"/>) because of the inclusion of more depleted <inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values from locations with higher altitudes during the kriging process.
By considering these two options for the spatial representation of <inline-formula><mml:math id="M86" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, we intend to assess the influence of spatial variability and uncertainty in the simulated outputs between two opposing cases i.e. raw isotopes representing the simplest approach and kriged isotopes derived from a more sophisticated method. While there are other possibilities for the spatial representation of <inline-formula><mml:math id="M87" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, our choice allows us to effectively address our research question regarding the effects on SAS models of tracer data in precipitation collected at a single location within the catchment or spatially interpolated from multiple sites.</p>
      <?pagebreak page2993?><p id="d1e2251">SAS model results are sensitive to the choice of the temporal resolution of input tracer data, and a finer resolution is generally recommended to achieve a satisfactory level of detail <xref ref-type="bibr" rid="bib1.bibx7" id="paren.44"/>. Additionally, a forward Euler scheme was employed to solve Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>), whose precision increases with high-frequency time steps.
For these reasons, we reconstructed daily <inline-formula><mml:math id="M88" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> estimates from monthly values with two interpolation schemes. First, we used a step function in which the values between two consecutive samples assumed the value of the last sample. Second, we used a sine interpolation due to the fact that <inline-formula><mml:math id="M89" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> samples typically exhibit pronounced seasonal variations with more depleted values in winter than in summer (Fig. <xref ref-type="fig" rid="Ch1.F2"/>). The sine-wave function has been used in several studies to describe temporal variation in <inline-formula><mml:math id="M90" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx67 bib1.bibx32 bib1.bibx3" id="paren.45"/>. The seasonal pattern of <inline-formula><mml:math id="M91" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values over a period of 1 year can be described as follows <xref ref-type="bibr" rid="bib1.bibx51" id="paren.46"/>:
            <disp-formula id="Ch1.E10" content-type="numbered"><label>10</label><mml:math id="M92" display="block"><mml:mrow><mml:msub><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mi>P</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:msub><mml:mi>a</mml:mi><mml:mi>P</mml:mi></mml:msub><mml:mo>⋅</mml:mo><mml:mi>cos⁡</mml:mi><mml:mo>(</mml:mo><mml:mn mathvariant="normal">2</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="italic">π</mml:mi><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>⋅</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:msub><mml:mi>b</mml:mi><mml:mi>P</mml:mi></mml:msub><mml:mo>⋅</mml:mo><mml:mi>sin⁡</mml:mi><mml:mo>(</mml:mo><mml:mn mathvariant="normal">2</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="italic">π</mml:mi><mml:mo>⋅</mml:mo><mml:mi>f</mml:mi><mml:mo>⋅</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:msub><mml:mi>k</mml:mi><mml:mi>P</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where <inline-formula><mml:math id="M93" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> and <inline-formula><mml:math id="M94" display="inline"><mml:mi>b</mml:mi></mml:math></inline-formula> are regression coefficients (–), <inline-formula><mml:math id="M95" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> is the time (decimal years), <inline-formula><mml:math id="M96" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula> is the frequency (yr<inline-formula><mml:math id="M97" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), and <inline-formula><mml:math id="M98" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> is the vertical offset of the isotope signal (‰).
The coefficients <inline-formula><mml:math id="M99" display="inline"><mml:mi>a</mml:mi></mml:math></inline-formula> and <inline-formula><mml:math id="M100" display="inline"><mml:mi>b</mml:mi></mml:math></inline-formula> were estimated by fitting Eq. (<xref ref-type="disp-formula" rid="Ch1.E10"/>) to monthly <inline-formula><mml:math id="M101" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values using the iteratively re-weighted least-squares (IRLS) estimation <xref ref-type="bibr" rid="bib1.bibx98" id="paren.47"/>. In our study, we reproduced the daily frequency isotopic data through the estimated regression coefficients of Eq. (<xref ref-type="disp-formula" rid="Ch1.E10"/>). Figure <xref ref-type="fig" rid="Ch1.F3"/> displays the daily kriged and raw <inline-formula><mml:math id="M102" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values simulated via step function and sine interpolation; by employing step function and sine interpolation as techniques to reconstruct tracer data in precipitation, we aim to analyze the effects on SAS-based results from two relatively simple, rather opposing approaches: one focusing on individual measurements and the other on seasonality.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><?xmltex \currentcnt{3}?><?xmltex \def\figurename{Figure}?><label>Figure 3</label><caption><p id="d1e2531">Predicted <inline-formula><mml:math id="M103" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in precipitation (kriged values as pink lines and raw values as yellow lines) via step function and sine interpolation.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023-f03.png"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS3">
  <label>3.3</label><title>Experimental design</title>
      <p id="d1e2561">In this study, different scenarios were used to quantify uncertainty in the modeled results. We tested 12 setups composed of three SAS functions (PLTI, PLTV, and BETATI), two temporal interpolations (step and sine function), and two spatial representations (raw and kriged values) of <inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (Table <xref ref-type="table" rid="Ch1.T1"/>). For each setup, we performed a Monte Carlo experiment by running the model with 10 000 parameter sets generated by Latin hypercube sampling <xref ref-type="bibr" rid="bib1.bibx68" id="paren.48"><named-content content-type="pre">LHS;</named-content></xref>. Model parameters and their search ranges are shown in Table <xref ref-type="table" rid="Ch1.T2"/>. A 5-year warm-up period (i.e. repetition of the input data) from February 2008 to January 2013 was performed to reduce the impact of model initialization. The period from February 2013 to May 2015 was used to infer behavioral parameters (i.e. parameter sets giving acceptable predictions) and, subsequently, to interpret model results. The initial concentration of <inline-formula><mml:math id="M105" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in storage was set to 9.2 ‰, coinciding with the mean <inline-formula><mml:math id="M106" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> over the study period.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1"><?xmltex \currentcnt{1}?><label>Table 1</label><caption><p id="d1e2622">List of model setups.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="3">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:thead>
       <oasis:row rowsep="1">

         <oasis:entry colname="col1">Setup</oasis:entry>

         <oasis:entry colname="col2">Interpolation</oasis:entry>

         <oasis:entry colname="col3">SAS function</oasis:entry>

       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>

         <oasis:entry colname="col1">a</oasis:entry>

         <?xmltex \mrwidth{2cm}?><oasis:entry rowsep="1" colname="col2" morerows="2" align="justify">step function <?xmltex \hack{\newline}?>kriged <inline-formula><mml:math id="M107" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>

         <oasis:entry colname="col3">PLTI</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">b</oasis:entry>

         <oasis:entry colname="col3">PLTV</oasis:entry>

       </oasis:row>
       <oasis:row rowsep="1">

         <oasis:entry colname="col1">c</oasis:entry>

         <oasis:entry colname="col3">BETATI</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">d</oasis:entry>

         <?xmltex \mrwidth{2cm}?><oasis:entry rowsep="1" colname="col2" morerows="2" align="justify">step function <?xmltex \hack{\newline}?>raw <inline-formula><mml:math id="M108" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>

         <oasis:entry colname="col3">PLTI</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">e</oasis:entry>

         <oasis:entry colname="col3">PLTV</oasis:entry>

       </oasis:row>
       <oasis:row rowsep="1">

         <oasis:entry colname="col1">f</oasis:entry>

         <oasis:entry colname="col3">BETATI</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">g</oasis:entry>

         <?xmltex \mrwidth{2cm}?><oasis:entry rowsep="1" colname="col2" morerows="2" align="justify">sine function <?xmltex \hack{\newline}?>kriged <inline-formula><mml:math id="M109" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>

         <oasis:entry colname="col3">PLTI</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">h</oasis:entry>

         <oasis:entry colname="col3">PLTV</oasis:entry>

       </oasis:row>
       <oasis:row rowsep="1">

         <oasis:entry colname="col1">i</oasis:entry>

         <oasis:entry colname="col3">BETATI</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">j</oasis:entry>

         <?xmltex \mrwidth{2cm}?><oasis:entry colname="col2" morerows="2" align="justify">sine function <?xmltex \hack{\newline}?>raw <inline-formula><mml:math id="M110" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>

         <oasis:entry colname="col3">PLTI</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">k</oasis:entry>

         <oasis:entry colname="col3">PLTV</oasis:entry>

       </oasis:row>
       <oasis:row>

         <oasis:entry colname="col1">l</oasis:entry>

         <oasis:entry colname="col3">BETATI</oasis:entry>

       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><?xmltex \gdef\@currentlabel{1}?></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><?xmltex \currentcnt{2}?><label>Table 2</label><caption><p id="d1e2847">Model parameters and search ranges.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="5">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="center"/>
     <oasis:colspec colnum="3" colname="col3" align="center"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1">SAS parameter</oasis:entry>
         <oasis:entry colname="col2">Symbol</oasis:entry>
         <oasis:entry colname="col3">Unit</oasis:entry>
         <oasis:entry colname="col4">Lower</oasis:entry>
         <oasis:entry colname="col5">Upper</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4">bound</oasis:entry>
         <oasis:entry colname="col5">bound</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M111" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">0.1</oasis:entry>
         <oasis:entry colname="col5">2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M112" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>Q</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">0.1</oasis:entry>
         <oasis:entry colname="col5">2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Discharge SAS parameter</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>Q</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">0.1</oasis:entry>
         <oasis:entry colname="col5">2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M114" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">0.1</oasis:entry>
         <oasis:entry colname="col5">2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M115" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">0.1</oasis:entry>
         <oasis:entry colname="col5">2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Evapotranspiration SAS parameter</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi mathvariant="normal">ET</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">–</oasis:entry>
         <oasis:entry colname="col4">0.1</oasis:entry>
         <oasis:entry colname="col5">2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Initial storage</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M117" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">mm</oasis:entry>
         <oasis:entry colname="col4">300</oasis:entry>
         <oasis:entry colname="col5">3000</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><?xmltex \gdef\@currentlabel{2}?></table-wrap>

      <p id="d1e3090">The informal likelihood of the Sequential Uncertainty Fitting <xref ref-type="bibr" rid="bib1.bibx1" id="paren.49"><named-content content-type="pre">SUFI-2;</named-content></xref> procedure was applied to account for uncertainty in the parameter sets and resulting modeled estimates. In SUFI-2, the uncertainty is represented by a uniform distribution, which is gradually reduced until a specific criterion is reached. In our study, we calibrated the values of model parameters until the predicted output matched the measured <inline-formula><mml:math id="M118" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> to a satisfactory level, defined by an objective function. As the objective function, we employed the Kling–Gupta efficiency <xref ref-type="bibr" rid="bib1.bibx33" id="paren.50"><named-content content-type="pre">KGE;</named-content></xref>, and once the criterion of KGE <inline-formula><mml:math id="M119" display="inline"><mml:mo>≥</mml:mo></mml:math></inline-formula> 0.5 was satisfied, we defined a set of behavioral solutions for each model setup.
However, as the aim of this study is to investigate the impact of various sources of uncertainty on simulated outputs, rather than to determine the best model setup, we decided to set a fixed sample size and narrow down those solutions generated by SUFI-2 in the previous step. Setting a fixed sample size ensures the comparability of results across the setups, as different sample sizes could influence the uncertainty analysis (i.e. the greater the number of behavioral solutions, the wider the uncertainty band). By fixing the sample size, we can still meet the requirement of a minimum acceptable KGE value (i.e. KGE <inline-formula><mml:math id="M120" display="inline"><mml:mo>≥</mml:mo></mml:math></inline-formula> 0.5). In this study, we determined the final behavioral solutions by using a fixed sample size that corresponds to the best 5 % parameter sets and modeled results in terms of the KGE.</p>
      <p id="d1e3133">To assess the range of possible behavioral solutions and understand the level of uncertainty associated with it, we calculated the 95 % confidence interval (CI) derived by computing the 2.5 % and 97.5 % percentile values of the cumulative distribution in the parameters and time series of output variables <xref ref-type="bibr" rid="bib1.bibx1" id="paren.51"/>. These percentile values represent the lower and upper bounds of the CI, respectively.
In our experimental setup, the main output variables were the in-stream <inline-formula><mml:math id="M121" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O signature and backward median transit time (TT<inline-formula><mml:math id="M122" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, in days, i.e. the time it takes for half of the water particles to leave the system as streamflow at the catchment outlet). Time series of TT<inline-formula><mml:math id="M123" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> were extracted directly from daily TTDs (Eq. <xref ref-type="disp-formula" rid="Ch1.E5"/>) and used as a metric for the streamflow age. This was done because TTDs are typically skewed with long tails <xref ref-type="bibr" rid="bib1.bibx54" id="paren.52"/>; hence, the median is often a more suitable metric than, for example, the MTT, as it is less impacted by the poor identifiability of the older water components <xref ref-type="bibr" rid="bib1.bibx12" id="paren.53"/>.</p>
</sec>
</sec>
<?pagebreak page2994?><sec id="Ch1.S4">
  <label>4</label><title>Results</title>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><?xmltex \opttitle{Simulated ${\protect\chem{\delta^{{18}}O}}$ in streamflow and model performance}?><title>Simulated <inline-formula><mml:math id="M124" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in streamflow and model performance</title>
      <p id="d1e3207">Modeled <inline-formula><mml:math id="M125" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values in streamflow (<inline-formula><mml:math id="M126" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) represented by the 95 % confidence interval (CI) in the ensemble solution are displayed in Fig. <xref ref-type="fig" rid="Ch1.F4"/>.
The results reveal how the predicted <inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values enveloped the measured isotopic signature by reproducing its seasonal fluctuations, with depleted (i.e. more negative) values in winter and enriched (i.e. less negative) values in summer. Although the behavioral parameter sets were able to capture the seasonal isotopic trend, they poorly reproduced the exact values; therefore, the ensemble simulations are characterized by a non-negligible uncertainty.</p>
      <p id="d1e3257">Figure <xref ref-type="fig" rid="Ch1.F4"/> shows the distinct effects of the interpolated input tracer data and model parameterization on the simulated <inline-formula><mml:math id="M128" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values.
The step function interpolation generated an erratic isotopic signature in streamflow with flashy fluctuations (Fig. <xref ref-type="fig" rid="Ch1.F4"/>a–f).
On the other hand, sine interpolation of <inline-formula><mml:math id="M129" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values yielded a smooth response in the simulated <inline-formula><mml:math id="M130" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values (Fig. <xref ref-type="fig" rid="Ch1.F4"/>g–l).
No significant visual distinction was found between kriged (Fig. <xref ref-type="fig" rid="Ch1.F4"/>a–c) and raw (Fig. <xref ref-type="fig" rid="Ch1.F4"/>d–f) <inline-formula><mml:math id="M131" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> samples when the step function interpolation was used, except for a slightly larger uncertainty observed with raw <inline-formula><mml:math id="M132" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> samples. Furthermore, when employing the sine interpolation and raw <inline-formula><mml:math id="M133" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values (Fig. <xref ref-type="fig" rid="Ch1.F4"/>j–l), the simulations overestimated the in-stream measurements in comparison with kriged values (Fig. <xref ref-type="fig" rid="Ch1.F4"/>g–i).
Finally, distinct SAS parameterizations did not produce remarkable differences in the simulated <inline-formula><mml:math id="M134" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values, although PLTV generally yielded simulations that better enveloped the measured isotopic signature (Fig. <xref ref-type="fig" rid="Ch1.F4"/>b, e, h, k).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4" specific-use="star"><?xmltex \currentcnt{4}?><?xmltex \def\figurename{Figure}?><label>Figure 4</label><caption><p id="d1e3392">Predicted <inline-formula><mml:math id="M135" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values in streamflow. The dark blue filled circles represent the observed data, and the dashed light blue lines and shaded areas represent the ensemble mean of all possible solutions and their range according to the 95 % CI, respectively.</p></caption>
          <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023-f04.png"/>

        </fig>

      <p id="d1e3415">Despite the differences in the predicted <inline-formula><mml:math id="M136" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values, all simulations can be considered satisfactory given the KGE values ranging between 0.55 and 0.72 across all tested setups (Fig. <xref ref-type="fig" rid="Ch1.F5"/>). This aforementioned model performance can be classified as intermediate <xref ref-type="bibr" rid="bib1.bibx91" id="paren.54"/> to good <xref ref-type="bibr" rid="bib1.bibx5 bib1.bibx88" id="paren.55"/>. When considering the best fit, the combination of step function interpolation and raw <inline-formula><mml:math id="M137" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values performed best. Additionally, PLTV generally yielded slightly better KGE values than PLTI or BETATI when grouping the setups with the same spatiotemporal interpolation of <inline-formula><mml:math id="M138" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. Differences in the mean KGEs were statistically insignificant (<inline-formula><mml:math id="M139" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> test with <inline-formula><mml:math id="M140" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> values <inline-formula><mml:math id="M141" display="inline"><mml:mo>&gt;</mml:mo></mml:math></inline-formula> 0.05) only between setups a–g, c–i–k, and j–l (Table <xref ref-type="table" rid="Ch1.T1"/>), as the mean KGE values were nearly identical; this largely agrees with the visual analysis (Fig. <xref ref-type="fig" rid="Ch1.F5"/>). Contrarily, the differences in the mean KGE values of the remaining setups were statistically significant (<inline-formula><mml:math id="M142" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> values <inline-formula><mml:math id="M143" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 0.05), indicating that the a priori methodological choices (i.e. interpolation techniques of <inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values and/or SAS parameterization) strongly impact the overall results. Nonetheless, this does not mean that we can clearly identify the most suitable setup, but there is a need to carefully analyze the multiple potential choices with respect to SAS parameterization and tracer data interpolations as well as to evaluate the uncertainty range in modeled predictions.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5" specific-use="star"><?xmltex \currentcnt{5}?><?xmltex \def\figurename{Figure}?><label>Figure 5</label><caption><p id="d1e3533">Box plots of model performance ranges in behavioral solutions. The letters on the <inline-formula><mml:math id="M145" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axis refer to the model setup type according to Table <xref ref-type="table" rid="Ch1.T1"/>. Box plots filled with the same colors represent model setups characterized by the same interpolation scheme in space and time. On each box, the central red line indicates the median, and the bottom and top edges of the box indicate the 25th and 75th percentiles, respectively, namely the interquartile range (IQR). The whiskers extend to the most extreme data points not considered outliers, which are the 25th percentile <inline-formula><mml:math id="M146" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula> 1.5 <inline-formula><mml:math id="M147" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> IQR and the 75th percentile <inline-formula><mml:math id="M148" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 1.5 <inline-formula><mml:math id="M149" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> IQR, respectively. The outliers are plotted individually using the red “<inline-formula><mml:math id="M150" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>” markers.
</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023-f05.png"/>

        </fig>

      <p id="d1e3587">Ranges of the behavioral SAS parameters for the tested setups are summarized in Table S1 in the Supplement. Parameters for the SAS functions of <inline-formula><mml:math id="M151" display="inline"><mml:mi>Q</mml:mi></mml:math></inline-formula> (i.e. <inline-formula><mml:math id="M152" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M153" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>Q</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M154" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>Q</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M155" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>, and <inline-formula><mml:math id="M156" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>) were different across the setups, although they were generally relatively narrow and well identified.
However, the behavioral parameters were better constrained when using the step function interpolation, as their 95 % CI was, on average, 34 % narrower than that provided by the sine interpolation, across all the SAS parameterizations.
The parameters <inline-formula><mml:math id="M157" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>Q</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M158" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula> were also better identified than <inline-formula><mml:math id="M159" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>Q</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M160" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>, as their 95 % CI was, on average, 56 % narrower, across all tested setups.
Conversely, there was no clear difference in the parameter ranges when using kriged or raw <inline-formula><mml:math id="M161" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values.
The evapotranspiration parameter (i.e. <inline-formula><mml:math id="M162" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi mathvariant="normal">ET</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) was poorly identified in all setups, as any value in the search range provided equally good results. The initial storage (i.e. <inline-formula><mml:math id="M163" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) was only partially constrained, as any value between 335 and 2895 mm was considered acceptable.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><title>Simulated transit times and model uncertainty</title>
      <?pagebreak page2995?><p id="d1e3740">Figure <xref ref-type="fig" rid="Ch1.F6"/> illustrates the 95 % CI of the behavioral solutions for the predicted median transit time (TT<inline-formula><mml:math id="M164" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>).
The results show that the model simulated largely different ranges of TT<inline-formula><mml:math id="M165" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> based on the tested setups. When using PLTI and BETATI (Fig. <xref ref-type="fig" rid="Ch1.F6"/>a, c, d, f, g, i, j, l), the 95 % CI was relatively stable with smaller fluctuations throughout the simulation period compared with PLTV (Fig. <xref ref-type="fig" rid="Ch1.F6"/>b, e, h, k).
However, minor differences emerged across the simulated TT<inline-formula><mml:math id="M166" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> as a result of the distinct interpolation techniques used for <inline-formula><mml:math id="M167" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. The 95 % CI of TT<inline-formula><mml:math id="M168" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> was, on average, 37 % larger, across all tested setups, when using raw <inline-formula><mml:math id="M169" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F6"/>d–f and j–l) rather than kriged <inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F6"/>a–c and g–i). This was especially visible when the step function was used (Fig. <xref ref-type="fig" rid="Ch1.F6"/>a–f). Moreover, the sine interpolation generated a 95 % CI of TT<inline-formula><mml:math id="M171" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> that was, on average, 62 % narrower across all tested setups (Fig. <xref ref-type="fig" rid="Ch1.F6"/>g–l) with respect to the step function (Fig. <xref ref-type="fig" rid="Ch1.F6"/>a–f). These differences were more evident for high-flow conditions where the 95 % CI of TT<inline-formula><mml:math id="M172" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> showed a significant reduction. In addition, the behavioral solutions obtained with the sine interpolation (Fig. <xref ref-type="fig" rid="Ch1.F6"/>g–l) were more skewed towards shorter mean TT<inline-formula><mml:math id="M173" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> values, across all tested setups, than those of the step function (Fig. <xref ref-type="fig" rid="Ch1.F6"/>a–f).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6" specific-use="star"><?xmltex \currentcnt{6}?><?xmltex \def\figurename{Figure}?><label>Figure 6</label><caption><p id="d1e3879">Predicted TT<inline-formula><mml:math id="M174" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> of streamflow. The dashed light blue lines and shaded areas represent the ensemble mean of all possible solutions and their range according to the 95 % CI, respectively.</p></caption>
          <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023-f06.png"/>

        </fig>

      <?pagebreak page2996?><p id="d1e3897">Behavioral solutions obtained with PLTV revealed a similar pattern regardless of the interpolation employed (Fig. <xref ref-type="fig" rid="Ch1.F6"/>b, e, h, k). Nonetheless, there was a noticeable difference in the 95 % CI of TT<inline-formula><mml:math id="M175" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> under distinct flow regimes. During low flows and dry periods (i.e. summer and autumn), the time series of predicted TT<inline-formula><mml:math id="M176" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> showed large uncertainties ranging at most between 259 and 1009 d across the different setups (Fig. <xref ref-type="fig" rid="Ch1.F6"/>e).
Conversely, during high flows (i.e. winter and spring), the 95 % CI was much narrower and varied at least between 126 and 154 d (Fig. <xref ref-type="fig" rid="Ch1.F6"/>h).
The large 95 % CI and the notable differences across the tested setups highlight the sensitivity and, in turn, the uncertainty in the predicted TT<inline-formula><mml:math id="M177" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> to the model parameterization, temporal interpolation of input data, hydrologic conditions, and nonspatially interpolated <inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>.</p>
      <p id="d1e3951">In general, the variability in the predicted TT<inline-formula><mml:math id="M179" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> was controlled by the hydrological state of the system (Fig. <xref ref-type="fig" rid="Ch1.F6"/>). High-discharge events reduced the TT<inline-formula><mml:math id="M180" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> values, whereas low-flow periods were associated with a longer estimated TT<inline-formula><mml:math id="M181" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>. This is expected, as streamflow during high (low) flows is dominated by near-surface runoff (groundwater) with shallow (deep) flow paths leading to a shorter (longer) TT<inline-formula><mml:math id="M182" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>.
Such differences were particularly visible with PLTV (Fig. <xref ref-type="fig" rid="Ch1.F6"/>b, e, h, k), as the exponent <inline-formula><mml:math id="M183" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> shifts the water selection preference over time as a function of the wet/dry conditions. This resulted in the variability in TT<inline-formula><mml:math id="M184" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> being more pronounced than that of PLTI and BETATI, whose SAS parameters for <italic>Q</italic> are constant over time.</p>
</sec>
<sec id="Ch1.S4.SS3">
  <label>4.3</label><title>Catchment-scale water release</title>
      <p id="d1e4032">SAS functions provided valuable insights into the catchment-scale water release dynamics. Figure <xref ref-type="fig" rid="Ch1.F7"/> presents the behavioral solutions releasing water of different ages and also shows that the catchment generally experienced a stronger affinity for releasing young water (i.e. <inline-formula><mml:math id="M185" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, or <inline-formula><mml:math id="M186" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M187" display="inline"><mml:mrow><mml:mi mathvariant="italic">β</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>), rather than old water (i.e. <inline-formula><mml:math id="M188" display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mi>Q</mml:mi></mml:msub><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, or <inline-formula><mml:math id="M189" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M190" display="inline"><mml:mrow><mml:mi mathvariant="italic">β</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>). These findings are in agreement with other studies in the upper Selke catchment <xref ref-type="bibr" rid="bib1.bibx102 bib1.bibx70" id="paren.56"/>. Nonetheless, there were differences in the water release scheme when comparing various combinations of SAS functions and spatiotemporal interpolation techniques of isotopes. The use of PLTV resulted in a substantial number of solutions, approximately 50 % of all behavioral solutions, suggesting a preference for both young and old water. On the other hand, only a few solutions showed affinity for old-water release, and this was more prominent when using the sine interpolation, raw <inline-formula><mml:math id="M191" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values, and PLTI across all tested setups.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7" specific-use="star"><?xmltex \currentcnt{7}?><?xmltex \def\figurename{Figure}?><label>Figure 7</label><caption><p id="d1e4137">Percentage of behavioral solutions releasing water of different ages.</p></caption>
          <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://hess.copernicus.org/articles/27/2989/2023/hess-27-2989-2023-f07.png"/>

        </fig>

</sec>
</sec>
<sec id="Ch1.S5">
  <label>5</label><title>Discussion</title>
<sec id="Ch1.S5.SS1">
  <label>5.1</label><title>Uncertainty in TTD modeling</title>
      <p id="d1e4163">In this study, we characterized the TTD uncertainty arising from some significant and critical aspects for the SAS modeling. These aspects are also the most directly linked to the data interpolation and SAS parameterization that we explored in this work. The uncertainty analysis was carried out across the 12 tested setups corresponding to different combinations of spatiotemporal data interpolation techniques and SAS parameterizations.
Our results show that the uncertainty (i.e. 95 % CI) of the simulated TT<inline-formula><mml:math id="M192" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F6"/>) was firmly dependent on the choice of model setup, as the 95 % CI was primarily sensitive to the type of SAS function, temporal interpolation, and spatial representation of <inline-formula><mml:math id="M193" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>.</p>
      <?pagebreak page2997?><p id="d1e4193">Uncertainty in the simulated TT<inline-formula><mml:math id="M194" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> differed considerably between time-invariant (i.e. PLTI and BETATI; Fig. <xref ref-type="fig" rid="Ch1.F6"/>a, c, d, f, g, i, j, l) and time-variant (i.e. PLTV; Fig. <xref ref-type="fig" rid="Ch1.F6"/>b, e, h, k) SAS functions; thus, a large sensitivity is associated with the choice of the SAS parameterization. For example, PLTI and BETATI explicitly assume constant water selection preference over time, as these functions do not consider the temporal variability in the catchment wetness. As a consequence, the resulting TT<inline-formula><mml:math id="M195" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> had a moderately stable 95 % CI with smaller fluctuations compared with those of PLTV.
On the other hand, including an explicit time dependence in the SAS function strongly affected the 95 % CI of TT<inline-formula><mml:math id="M196" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>. Notably, PLTV produced a wider 95 % CI during low-flow conditions, which can hinder the TTDs ability to provide robust insights into flow and solute transport behaviors in the study area during low-flow conditions. This highlights the need to further constrain PLTV with additional data, which could involve obtaining tracer data at a finer resolution or additional information on the evapotranspiration and initial storage.
In addition, the exceptionally old flow components associated with a very large 95 % CI of TT<inline-formula><mml:math id="M197" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> might be a distortion of the actual TT<inline-formula><mml:math id="M198" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> values, which can usually be more reliably estimated using radioactive tracers than with stable isotopes <xref ref-type="bibr" rid="bib1.bibx96" id="paren.57"/>. Hence, PLTV-based TT<inline-formula><mml:math id="M199" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> greater than the observed period (828 d) should be interpreted carefully.
It is important to note that we discussed the fractional SAS (fSAS) functions in this study, but another form of the SAS functions, such as the rank SAS (rSAS) functions, may have different uncertainty. This is mainly due to the difference in how the storage is considered: fSAS functions are expressed as function of the normalized age-ranked storage, which is equal to the cumulative residence time, whereas rSAS functions depend on the age-ranked storage, which is the volume of water in storage ranked from youngest to oldest <xref ref-type="bibr" rid="bib1.bibx34" id="paren.58"/>.</p>
      <p id="d1e4261">Likewise, the high-frequency reconstruction of <inline-formula><mml:math id="M200" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> from monthly samples via interpolation created further uncertainty.
The sine interpolation effectively captured the dominant features of the observed <inline-formula><mml:math id="M201" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, such as seasonality. Consequently, sine interpolation successfully reproduced the seasonal trend in in-stream <inline-formula><mml:math id="M202" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, although simulations overestimated the measurements (Fig. <xref ref-type="fig" rid="Ch1.F4"/>g–l). On the other hand, sine interpolation poorly reproduced rainfall isotopes during short-term flashy events and missed detailed characteristics of the tracer dataset by smoothing the variability in the observed <inline-formula><mml:math id="M203" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). As a result, high values of <inline-formula><mml:math id="M204" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are underestimated, whereas low values are overestimated. It is critical to recognize these limitations when interpreting modeling results, as uncertainty in the simulated <inline-formula><mml:math id="M205" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> may conceal a more pronounced hydrological response of the system <xref ref-type="bibr" rid="bib1.bibx28 bib1.bibx17 bib1.bibx40" id="paren.59"/>.
Contrarily, step function interpolation preserved the maxima in the monthly observed <inline-formula><mml:math id="M206" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values by capturing their variation correctly (Fig. <xref ref-type="fig" rid="Ch1.F3"/>). Simulations showed a better fit with measured in-stream <inline-formula><mml:math id="M207" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F4"/>a–f) and higher model performance (Fig. <xref ref-type="fig" rid="Ch1.F5"/>). However, combining step function with raw <inline-formula><mml:math id="M208" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> resulted in larger uncertainty in the simulated TT<inline-formula><mml:math id="M209" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F6"/>d–f). This reflects the need for a comprehensive exploration of the uncertainty range, rather than relying solely on the goodness of fit.
Overall, the choice between step function and sine interpolation largely affected the reconstructed input data (Fig. <xref ref-type="fig" rid="Ch1.F3"/>), leading to significant differences in the simulated TT<inline-formula><mml:math id="M210" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> and associated uncertainty.
It is important to note that alternative methods, such as generalized additive models <xref ref-type="bibr" rid="bib1.bibx23" id="paren.60"><named-content content-type="pre">GAMs;</named-content></xref>, offer other options for interpolating tracer data. We conducted further tests with the SAS model using a GAM to reconstruct both kriged and raw <inline-formula><mml:math id="M211" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> using smoothing functions; this provides a more sophisticated approach than the intuitive methods used in this study. However, the results, available in the Supplement, show that while a GAM provided more detailed reconstructed input tracer data (Fig. S1), it did not significantly alter the SAS-based results (Figs. S2, S3) or yield any new insights or conclusions about uncertainty with respect to using step function and sine interpolation. Therefore, we conclude that, while highly resolved input data may seem appealing, they do not necessarily lead to substantial benefits for the SAS-based output, supposedly due to the conceptual simplifications in the SAS model.</p>
      <p id="d1e4461">The spatial representation of <inline-formula><mml:math id="M212" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values had limited impact on the overall pattern of simulated TT<inline-formula><mml:math id="M213" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, as the time series were comparable with both kriged (Fig. <xref ref-type="fig" rid="Ch1.F6"/>a–c and g–i) and raw (Fig. <xref ref-type="fig" rid="Ch1.F6"/>d–f and j–l) <inline-formula><mml:math id="M214" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. Nonetheless, the spatial interpolation of <inline-formula><mml:math id="M215" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> from different locations resulted in a reduction in the uncertainty in the TT<inline-formula><mml:math id="M216" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, which was particularly evident with the step function (Fig. <xref ref-type="fig" rid="Ch1.F6"/>a–f). This difference may be attributed to the fact that the upper Selke is a large (mesoscale) catchment with a substantial gradient in elevation, and, as a consequence, measurement for <inline-formula><mml:math id="M217" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> from only one location may be generally overly simplistic.
This finding highlights the importance of considering not only the model performance (Fig. <xref ref-type="fig" rid="Ch1.F5"/>; raw values with a step function interpolation produced higher KGE values) but also the uncertainty range in predicted TT<inline-formula><mml:math id="M218" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>.</p>
      <p id="d1e4565">Finally, we found that the uncertainty was larger under dry conditions when lower flow and longer TT<inline-formula><mml:math id="M219" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> were observed. This was especially visible when using the time-variant SAS function (Fig. <xref ref-type="fig" rid="Ch1.F6"/>b, e, h, k). It might be due to the fact that, under wet conditions, there is a high level of hydrologic connectivity within the catchment <xref ref-type="bibr" rid="bib1.bibx4 bib1.bibx18 bib1.bibx42" id="paren.61"/>, which results in nearly all flow paths being active and contributing to the streamflow. This, ultimately, may make TT<inline-formula><mml:math id="M220" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> values easier to constrain. Conversely, under dry conditions, when usually only longer flow paths carrying older water are active <xref ref-type="bibr" rid="bib1.bibx84 bib1.bibx45" id="paren.62"/>, water partially flows through a drier soil zone where flow is more erratic (i.e. flow directions and patterns can vary widely) as the conductivity is controlled by soil moisture. As a result,<?pagebreak page2998?> wet areas can be patchy and water flows preferentially at certain locations only, as opposed to spatially uniform flow through the soil matrix; this might make it more challenging to constrain older water ages.
Similarly, <xref ref-type="bibr" rid="bib1.bibx12" id="text.63"/> found higher uncertainty in the simulated SAS-based median water ages during drier periods, potentially due to higher uncertainty in the total storage. Moreover, non-SAS function studies have observed major uncertainties and deviations from observations in lumped modeled results during low-flow conditions <xref ref-type="bibr" rid="bib1.bibx57" id="paren.64"/>. This was primarily due to the lack of spatial variability in the catchment characteristics in lumped models, which is a critical factor controlling low-flow regimes in rivers.</p>
      <p id="d1e4601">The dissimilarities in the simulated  TT<inline-formula><mml:math id="M221" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> across the tested setups underline the importance of accounting for uncertainty in model-based TTDs. The uncertainty analysis with SUFI-2 performed in this study was essential to best describe the parameter identifiability and bounds of the behavioral solutions of each output variable.
Furthermore, our results highlight the importance of gaining tracer datasets of good quality (i.e. tracer data with a finer temporal resolution), considering the spatial variability in the isotopic composition in precipitation, and, possibly, employing a model parameterization that best describes the catchment-specific storage and release dynamics. The last point can be defined according to a precise conceptual knowledge of the catchment’s functioning and information from previous studies in similar catchments.</p>
</sec>
<sec id="Ch1.S5.SS2">
  <label>5.2</label><title>TTD modeling: advantages and limitations</title>
      <p id="d1e4621">Our results provide visually plausible seasonal fluctuations in the predicted <inline-formula><mml:math id="M222" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>Q</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> samples (Fig. <xref ref-type="fig" rid="Ch1.F4"/>) and satisfactory KGE values (Fig. <xref ref-type="fig" rid="Ch1.F5"/>), despite the uncertainty arising from model inputs, structure, and parameters.
The good match with observations provides confidence in the simulated TT<inline-formula><mml:math id="M223" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> for the upper Selke catchment. The magnitude of the uncertainty resulting from different setups cannot be generalized, but the overall approach for uncertainty assessment presented here could be extended to other areas and TTD studies. However, we recognize some limitations and indicate below possible reasons and, in turn, improvements that future work could achieve.</p>
      <p id="d1e4653">First, the limited length of the <inline-formula><mml:math id="M224" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> time series might not describe the system accurately; hence, implementing longer time series could improve the parameter identifiability and provide a more accurate estimation of the TTDs.
Second, this study relied on stable water isotopes, which might underestimate the tails of the TTDs <xref ref-type="bibr" rid="bib1.bibx85 bib1.bibx83" id="paren.65"/>, although recent works have contested this <xref ref-type="bibr" rid="bib1.bibx100" id="paren.66"/>. Possible advancements could be reached by using decaying tracers varying over a longer timescale than stable water isotopes <xref ref-type="bibr" rid="bib1.bibx86 bib1.bibx69" id="paren.67"><named-content content-type="pre">e.g. tritium;</named-content></xref> and imparting more information on old water.
Next, future work should retrieve more information on the evapotranspiration ET and initial storage <inline-formula><mml:math id="M225" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, whose parameters were poorly identified. However, this issue is common in transport studies that rely on measurements of in-stream stable water isotopes <xref ref-type="bibr" rid="bib1.bibx12 bib1.bibx23" id="paren.68"/>. As a way forward, information on the ET isotopic compositions might help better constrain ET parameters and assess their affinity for young/old water. Regarding constraining the range of <inline-formula><mml:math id="M226" display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, further information can be gained from geophysical surveys in the study areas or groundwater modeling as well as by using decaying isotopes <xref ref-type="bibr" rid="bib1.bibx96" id="paren.69"/>.</p>
</sec>
<sec id="Ch1.S5.SS3">
  <label>5.3</label><title>Implications of TTD uncertainties</title>
      <p id="d1e4717">This study characterized the uncertainty in TTDs, which summarize the catchment's hydrologic transport behavior and, therefore, comprise decisive information for water managers. The value of TT<inline-formula><mml:math id="M227" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> has relevant implications for both water quantity and quality, as does its uncertainty. The larger the 95 % CI in the simulated TT<inline-formula><mml:math id="M228" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, the greater the difference in the TT<inline-formula><mml:math id="M229" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> values, which, ultimately, implies distinct hydrological processes, water availability, groundwater recharge, and solute export dynamics <xref ref-type="bibr" rid="bib1.bibx66" id="paren.70"/>.</p>
      <p id="d1e4750">For example, knowing the TTD and its uncertainty may be crucial for characterizing the catchment's response to climatic change <xref ref-type="bibr" rid="bib1.bibx101" id="paren.71"/>. Considering the increasing severity of droughts in the past decades <xref ref-type="bibr" rid="bib1.bibx24" id="paren.72"/>, a catchment with a shorter TT<inline-formula><mml:math id="M230" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> and a dominant release of young water might be more affected by droughts than a catchment with a longer TT<inline-formula><mml:math id="M231" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, which means that its stream is fed by relatively old water sources. Therefore, a short TT<inline-formula><mml:math id="M232" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> reveals a low drought resilience of the catchment and limited water availability, which could limit streamflow generation processes and change the in-stream water quality status during drought periods <xref ref-type="bibr" rid="bib1.bibx103" id="paren.73"/>.
Likewise, TTD uncertainty may affect the understanding of the water infiltration rate, hydrological processes, and aquifer recharge, as a shorter TT<inline-formula><mml:math id="M233" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> suggests that water is quickly routed to the catchment outlet rather than infiltrating deeply into the groundwater.
Finally, TTD uncertainty can have an impact on the quantification of the modern groundwater age, i.e. groundwater younger than 50 years <xref ref-type="bibr" rid="bib1.bibx13" id="paren.74"/>. According to <xref ref-type="bibr" rid="bib1.bibx44" id="text.75"/>, the correct identification of modern groundwater abundance and distribution can help determine its renewal <xref ref-type="bibr" rid="bib1.bibx60 bib1.bibx43" id="paren.76"/>, groundwater wells and depths most likely to contain contaminants <xref ref-type="bibr" rid="bib1.bibx95 bib1.bibx73" id="paren.77"/>, and the part of the aquifer flushed more rapidly.</p>
      <p id="d1e4811">Uncertainty in TTDs also impacts on assessing the fate of dissolved solutes, such as nitrates <xref ref-type="bibr" rid="bib1.bibx107 bib1.bibx70 bib1.bibx71 bib1.bibx65" id="paren.78"/>, pesticides <xref ref-type="bibr" rid="bib1.bibx38 bib1.bibx63" id="paren.79"/>, and chlorides <xref ref-type="bibr" rid="bib1.bibx53 bib1.bibx9" id="paren.80"/>. These solutes constitute a crucial source of diffuse water pollution in agricultural areas <xref ref-type="bibr" rid="bib1.bibx46 bib1.bibx59" id="paren.81"/>, as they<?pagebreak page2999?> are spread on the soil in large quantities, especially during the growing season.
The exposure time of solutes with the soil matrix has strong consequences for biogeochemical reactions, such as denitrification in the case of nitrates <xref ref-type="bibr" rid="bib1.bibx56 bib1.bibx59" id="paren.82"/>. A short TT<inline-formula><mml:math id="M234" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> suggests that water can be rapidly conveyed to the stream network <xref ref-type="bibr" rid="bib1.bibx54" id="paren.83"/>, with limited time for denitrification. This explains the elevated in-stream concentration and short-term impact of nitrate export compared with that of a longer TT<inline-formula><mml:math id="M235" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, which is typically associated with old-water release and a low nitrate concentration <xref ref-type="bibr" rid="bib1.bibx70" id="paren.84"/>.
Similarly, pesticide transport is highly affected by the TTD uncertainty, as a long TT<inline-formula><mml:math id="M236" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> suggests little pesticide degradation due to decreased microbial activity along deeper flow paths <xref ref-type="bibr" rid="bib1.bibx80" id="paren.85"/>. In other cases, a shorter TT<inline-formula><mml:math id="M237" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> may limit the time for degradation, causing a peak in the in-stream concentration <xref ref-type="bibr" rid="bib1.bibx61" id="paren.86"/>.
Overall, a longer TT<inline-formula><mml:math id="M238" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> can delay or buffer the catchment's reactive solute response at the outlet <xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx94" id="paren.87"/>. This creates a long-term effect of hydrological legacies and a continuous problem with diffuse pollution of nitrates <xref ref-type="bibr" rid="bib1.bibx31 bib1.bibx102" id="paren.88"/> and pesticides <xref ref-type="bibr" rid="bib1.bibx62" id="paren.89"/>, which can persist in the catchment for several years.
Finally, TTD uncertainties also play an important role in chloride transport, although chlorides are commonly known to be conservative <xref ref-type="bibr" rid="bib1.bibx89" id="paren.90"/>. A short TT<inline-formula><mml:math id="M239" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> may indicate rapid chloride mobilization, whereas a long TT<inline-formula><mml:math id="M240" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> implies chloride persistence in groundwater; therefore, chloride accumulates and is released at lower rates, with impacts on the ecosystem functions, vegetation uptake, and metabolism <xref ref-type="bibr" rid="bib1.bibx105" id="paren.91"/>.</p>
      <p id="d1e4922">Understanding the uncertainty in TTDs is crucial for the aforementioned implications. While previous studies have used only a specific SAS function and/or specific tracer data interpolation technique in time and space, here we show that there could be a wide range of different results in terms of water ages, model performance, and parameter uncertainty. This is due to the specific choice regarding SAS parameterization and tracer data interpolation. With this, we want to convey that uncertainty is omnipresent in TTD-based models, and we need to recognize it, especially when dealing with sparse tracer data and multiple choices for model parameterization. Therefore, we want to encourage future studies to explore these uncertainties in other catchments and different geophysical settings, with the final aim to investigate whether these uncertainties may affect the conclusions of water quantity and quality studies for management purposes.</p>
</sec>
</sec>
<sec id="Ch1.S6" sec-type="conclusions">
  <label>6</label><title>Conclusions</title>
      <p id="d1e4934">This study explored the uncertainty in TTDs of streamflow, resulting from 12 model setups obtained from different SAS parameterizations (i.e. PLTI, PLTV, and BETATI), and reconstruction of the precipitation isotopic signature in time and space via interpolation (step function vs. sine fit and raw vs. kriged values).</p>
      <p id="d1e4937">We found satisfactory KGE values, whose differences across the tested setups were statistically significant, meaning that the choice of the setup matters. As a consequence, distinct setups led to considerably different simulated TT<inline-formula><mml:math id="M241" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> values.
The choice between using time-variant or time-invariant SAS functions was crucial, as the time-invariant functions generated moderate fluctuations in the 95 % CI of the estimated TT<inline-formula><mml:math id="M242" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> because of the constant water selection preference over time. On the other hand, the time-variant SAS function captured the dynamics of the catchment wetness, resulting in more pronounced fluctuations in TT<inline-formula><mml:math id="M243" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>. However, the time-variant SAS function also produced a larger 95 % CI in TT<inline-formula><mml:math id="M244" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, notably during drier periods, which might indicate the need to constrain the function with additional data (e.g. finer tracer data resolution and/or information on evapotranspiration and storage).
Significant differences in TT<inline-formula><mml:math id="M245" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> were observed depending on the employed temporal interpolations. Results from the sine interpolation produced a smaller uncertainty in TT<inline-formula><mml:math id="M246" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, with the time series skewed towards smaller values. However, such results must be interpreted carefully, as the sine interpolation poorly reproduced flashy events in precipitation, thus indicating that some more dynamic transport processes were not fully considered. Conversely, the step function interpolation resulted in a larger uncertainty in the TT<inline-formula><mml:math id="M247" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>, but it was able to better reproduce the measured <inline-formula><mml:math id="M248" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>P</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> data by capturing the peak values, as opposed to the sine interpolation.
Dry conditions were another reason for uncertainty, as indicated by the high variance in the simulated TT<inline-formula><mml:math id="M249" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula> values, which is potentially attributed to the water preferentially moving at certain locations, making wet areas patchy, so it may be more challenging to accurately constrain older water ages.
Finally, there was comparable pattern in the modeled results when using kriged vs. raw isotopes, but the kriged values yielded an uncertainty reduction in TT<inline-formula><mml:math id="M250" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">50</mml:mn></mml:msub></mml:math></inline-formula>. This highlights the potential advantage of spatially interpolated values over a single measurement representative of the entire area, particularly in a mesoscale catchment that varies with respect to elevation.</p>
      <p id="d1e5038">These findings provide new insights into TTD uncertainty when high-frequency tracer data are missing and the SAS framework is used. Regardless of the degree of efficiency or uncertainty, the decision on which setup is more plausible depends on the best conceptual knowledge of the catchment functioning.
We consider the presented approach to be potentially applicable to other studies to enable a better characterization of TTD uncertainty, improve TTD simulations and, ultimately, inform water management. These aspects are particularly crucial in view of increasingly extreme climatic conditions and worsening water pollution under global change.</p>
</sec>

      
      </body>
    <back><notes notes-type="codedataavailability"><title>Code and data availability</title>

      <?pagebreak page3000?><p id="d1e5045">The version of the model used in this study (v1.0) and its documentation are available at <uri>https://github.com/pbenettin/tran-SAS</uri> (last access: August 2020) and <ext-link xlink:href="https://doi.org/10.5281/zenodo.1203600" ext-link-type="DOI">10.5281/zenodo.1203600</ext-link> <xref ref-type="bibr" rid="bib1.bibx8" id="paren.92"/>. The iteratively re-weighted least-squares (IRLS) method used to obtain the modeled daily kriged and raw isotope (<inline-formula><mml:math id="M251" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>) in precipitation information with the sine interpolation is presented at <ext-link xlink:href="https://doi.org/10.5194/hess-22-3841-2018" ext-link-type="DOI">10.5194/hess-22-3841-2018</ext-link> <xref ref-type="bibr" rid="bib1.bibx98" id="paren.93"/>. The hydroclimatic time series, <inline-formula><mml:math id="M252" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> data, and interpolated <inline-formula><mml:math id="M253" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> time series can be accessed at <ext-link xlink:href="https://doi.org/10.5281/zenodo.8121108" ext-link-type="DOI">10.5281/zenodo.8121108</ext-link> <xref ref-type="bibr" rid="bib1.bibx19" id="paren.94"/>.</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e5109">The supplement related to this article is available online at: <inline-supplementary-material xlink:href="https://doi.org/10.5194/hess-27-2989-2023-supplement" xlink:title="pdf">https://doi.org/10.5194/hess-27-2989-2023-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e5118">AB conducted the model simulations, carried out the analysis, interpreted the results, and wrote the original draft of the paper. SRL and RK designed and conceptualized the study and provided data for model simulations. TVN provided technical support for modeling and helped organize the structure and content of the paper. AB, SRL, RK, and TVN conceived the methodology and experimental design. All co-authors helped AB interpret the results. All authors contributed to the review, final writing, and finalization of this work.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e5124">At least one of the (co-)authors is a member of the editorial board of <italic>Hydrology and Earth System Sciences</italic>. The peer-review process was guided by an independent editor, and the authors also have no other competing interests to declare.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d1e5133">Publisher’s note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e5139">The authors thank the Helmholtz Centre for Environmental Research – UFZ of the Helmholtz Association for funding this study; the German Weather Service and the mHM model team for providing the necessary input data; and the developers of the <italic>tran</italic>-SAS model and IRLS code for making them publicly available.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e5147">The article processing charges for this open-access publication were covered by the Helmholtz Centre for Environmental Research – UFZ.</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e5154">This paper was edited by Laurent Pfister and reviewed by Ciaran Harman and one anonymous referee.</p>
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