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  <front>
    <journal-meta><journal-id journal-id-type="publisher">BG</journal-id><journal-title-group>
    <journal-title>Biogeosciences</journal-title>
    <abbrev-journal-title abbrev-type="publisher">BG</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Biogeosciences</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1726-4189</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/bg-23-5549-2026</article-id><title-group><article-title>Estimation of the degree of decomposition of peat and past net primary production from mid-infrared spectra</article-title><alt-title>Estimation of peat <inline-formula><mml:math id="M1" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and past NPP from MIRS</alt-title>
      </title-group>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1 aff2">
          <name><surname>Teickner</surname><given-names>Henning</given-names></name>
          <email>henning.teickner@uni-muenster.de</email>
        <ext-link>https://orcid.org/0000-0002-3993-1182</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Arsenault</surname><given-names>Julien</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-7840-1838</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Gałka</surname><given-names>Mariusz</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-8906-944X</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Knorr</surname><given-names>Klaus-Holger</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-4175-0214</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Ecohydrology &amp; Biogeochemistry Group, Institute of Landscape Ecology, University of Münster, 48149 Münster, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Spatiotemporal Modelling Lab, Institute for Geoinformatics, University of Münster, 48149 Münster, Germany</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Département des Sciences biologiques, Université du Québec à Montréal, Montréal, H2X 1Y4, Canada</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>University of Lodz, Faculty of Biology and Environmental Protection, Department of Biogeography, Paleoecology and Nature Conservation, Banacha 1/3, 90-237 Łodz, Poland</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Henning Teickner (henning.teickner@uni-muenster.de)</corresp></author-notes><pub-date><day>12</day><month>August</month><year>2026</year></pub-date>
      
      <volume>23</volume>
      <issue>15</issue>
      <fpage>5549</fpage><lpage>5570</lpage>
      <history>
        <date date-type="received"><day>22</day><month>November</month><year>2025</year></date>
           <date date-type="rev-request"><day>23</day><month>December</month><year>2025</year></date>
           <date date-type="rev-recd"><day>12</day><month>July</month><year>2026</year></date>
           <date date-type="accepted"><day>19</day><month>July</month><year>2026</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2026 Henning Teickner et al.</copyright-statement>
        <copyright-year>2026</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://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026.html">This article is available from https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026.html</self-uri><self-uri xlink:href="https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026.pdf">The full text article is available as a PDF file from https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026.pdf</self-uri>
      <abstract><title>Abstract</title>

      <p id="d2e136">The degree of decomposition of peat (<inline-formula><mml:math id="M2" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>) is useful to understand peatland degradation and peat accumulation, to reconstruct past net primary production (NPP), and to improve peatland models. None of the available decomposition indicators allows to estimate <inline-formula><mml:math id="M3" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> with sufficient accuracy. We suggest prediction of <inline-formula><mml:math id="M4" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> measured in litterbag experiments from mid-infrared spectra (MIRS) as a novel decomposition indicator, <inline-formula><mml:math id="M5" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, and compute prediction models for <inline-formula><mml:math id="M6" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with available litterbag experiments and litter data from diverse species from the Peatland Mid-Infrared Database. For individual litter samples, the prediction models fit the data well, have reasonable prediction errors (average RMSE between 0.09–0.12 <inline-formula><mml:math id="M7" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>), and neither confound differences in litter chemistry nor differences in silicate contents with decomposition losses. We show that an underestimation of <inline-formula><mml:math id="M8" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> by <inline-formula><mml:math id="M9" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> matches theoretical expectations; it can therefore be compensated, using plant macrofossil analysis data as a first approximation to mass fractions of peat components and a simple mixing model, or it can be avoided with component-specific measurements instead of bulk measurements. This allows to estimate <inline-formula><mml:math id="M10" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of peat samples and of dominant litter types and therefore also to reconstruct past NPP. To illustrate the approach, we analyze three cores from European mountain bogs and discuss how it can be used to improve process models and support restoration of peatlands. In particular, we test previously suggested relations between the saturated hydraulic conductivity and <inline-formula><mml:math id="M11" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, illustrate how <inline-formula><mml:math id="M12" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> measured on individual litter types may allow to use peat cores as natural litterbag experiments, and define reference states for <inline-formula><mml:math id="M13" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and NPP for the three analyzed peat cores. The method requires further validation by future studies. Improvements to reduce prediction errors of the approach require more diverse litterbag data, especially woody species and more decomposed litter. Further improvements can be achieved with measurements of MIRS on individual macrofossil types instead of bulk measurements, and an improved estimation of mass fractions of macrofossil types in peat samples instead of assuming that macrofossil abundances equal macrofossil masses.</p>
  </abstract>
    
<funding-group>
<award-group id="gs1">
<funding-source>Deutsche Forschungsgemeinschaft</funding-source>
<award-id>KN 929/23-1</award-id>
<award-id>PE 1632/18-1</award-id>
</award-group>
</funding-group>
</article-meta>
  </front>
<body>
      

      
<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d2e258">Peatland mass and carbon balance are the difference of net primary production (NPP) as mass input and of decomposition as mass output. Theory and modeling studies suggest a complex feedback between decomposition and net peat accumulation <xref ref-type="bibr" rid="bib1.bibx6 bib1.bibx9 bib1.bibx42 bib1.bibx83 bib1.bibx37" id="paren.1"/>. As a direct effect, decomposition decreases net peat accumulation because mass is lost from the system, but as an indirect effect, this mass loss decreases peat height, porosity, and hydraulic conductivity, which can increase surface wetness and therefore may increase litter production and decrease decomposition over longer time periods. Under some conditions, more decomposition can therefore increase future net peat accumulation <xref ref-type="bibr" rid="bib1.bibx49" id="paren.2"><named-content content-type="pre">e.g.</named-content></xref>. Therefore, if we could accurately describe how decomposition is controlled by environmental conditions, we could improve both reconstructions of past and predictions of future peatland dynamics.</p>
      <p id="d2e269">When analyzing peat accumulation and decomposition processes, an important quantity is the degree of decomposition (<inline-formula><mml:math id="M14" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>), the fraction of initial mass that was lost due to decomposition. It is directly measured in litterbag experiments and allows to estimate decomposition rates and how they are controlled by environmental conditions. Peatland models use these estimates to simulate decomposition in peatlands for decades to millenia <xref ref-type="bibr" rid="bib1.bibx29" id="paren.3"><named-content content-type="pre">e.g.</named-content></xref>. However, litterbag experiments only cover short time periods which leads to imprecise estimates for parameters that take effect only over longer time periods, such as the slow-down of decomposition due to increasing recalcitrance of the material left behind <xref ref-type="bibr" rid="bib1.bibx28" id="paren.4"/>. The degree of decomposition is also used to estimate mechanical and hydrological properties that control the ecohydrological feedback, such as the Young's modulus <xref ref-type="bibr" rid="bib1.bibx37 bib1.bibx38" id="paren.5"/>, bulk density <xref ref-type="bibr" rid="bib1.bibx29" id="paren.6"/>, and saturated hydraulic conductivity <xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx42 bib1.bibx44" id="paren.7"/>, but these relations have only been tested against qualitative decomposition indicators <xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx44" id="paren.8"/>, if at all. Estimates for <inline-formula><mml:math id="M15" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of peat are also useful to disentangle peat accumulation scenarios: an unfortunate consequence of the ecohydrological feedback is that both shallow and deep water table levels may lead to very similar peat heights and masses, two variables often used to test peatland models, but litter production, decomposition losses, the net mass balance, and <inline-formula><mml:math id="M16" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> differ between these contrasting scenarios <xref ref-type="bibr" rid="bib1.bibx51" id="paren.9"/>. For this reason, estimates of <inline-formula><mml:math id="M17" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for peat samples would be useful to distinguish between these scenarios and to obtain more accurate estimates for process rates <xref ref-type="bibr" rid="bib1.bibx51" id="paren.10"/>. Finally, if <inline-formula><mml:math id="M18" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is known for a peat sample, one can directly estimate the initial mass of the sample as <inline-formula><mml:math id="M19" display="inline"><mml:mrow><mml:mi>m</mml:mi><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, where <inline-formula><mml:math id="M20" display="inline"><mml:mi>m</mml:mi></mml:math></inline-formula> is the final mass of the sample. The NPP can be computed from the initial mass if the peat core is dated and roots are not dominant in peat formation. Thus, <inline-formula><mml:math id="M21" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is a central quantity when estimating parameters and reconstructing process rates.</p>
      <p id="d2e369">It is currently not possible to measure <inline-formula><mml:math id="M22" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for peat samples. Direct measurements of <inline-formula><mml:math id="M23" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> are currently only possible in litterbag experiments. For peat, several measurable properties (decomposition indicators) have been suggested to estimate differences in <inline-formula><mml:math id="M24" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. Currently, only the ash residue method <xref ref-type="bibr" rid="bib1.bibx33 bib1.bibx34" id="paren.11"><named-content content-type="pre">e.g.</named-content></xref> allows to estimate <inline-formula><mml:math id="M25" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> on an absolute scale, but this method has large errors <xref ref-type="bibr" rid="bib1.bibx32" id="paren.12"/> and indirectly presupposes that one already knows the initial mass of a sample (we abbreviate <inline-formula><mml:math id="M26" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimated with the ash residue method as <inline-formula><mml:math id="M27" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>ARM</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>). All other decomposition indicators we are aware of have only been used to estimate qualitative differences in the degree of decomposition of peat <xref ref-type="bibr" rid="bib1.bibx12 bib1.bibx91" id="paren.13"/>. Problems in the application of decomposition indicators are that the exact relation to <inline-formula><mml:math id="M28" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is unknown, that confounding variables are known to weaken or to reverse the relation to <inline-formula><mml:math id="M29" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, or worse, potential confounders are unknown, and that the values of decomposition indicators may be highly variable already for undecomposed peat because of differences in litter chemistry <xref ref-type="bibr" rid="bib1.bibx12 bib1.bibx57 bib1.bibx35 bib1.bibx37 bib1.bibx17 bib1.bibx61 bib1.bibx68" id="paren.14"><named-content content-type="pre">e.g.</named-content></xref>.</p>
      <p id="d2e450">To address these problems with measuring <inline-formula><mml:math id="M30" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, we suggest to define properties of an ideal decomposition indicator and based on this develop a decomposition indicator that has these properties. An ideal decomposition indicator is linearly related to <inline-formula><mml:math id="M31" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, well tested against litterbag data, does not confound differences in litter chemistry of undecomposed litter with decomposition, and is robust against other potential confounding factors, in particular mineral contents and mixing different litter types.</p>
      <p id="d2e468">To develop such a decomposition indicator, we suggest to develop a model that predicts <inline-formula><mml:math id="M32" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> measured in litterbag experiments from mid-infrared spectra (MIRS). Predictions by these models are the suggested decomposition indicator, <inline-formula><mml:math id="M33" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>. Such a model may fulfill the requirements of an ideal decomposition indicator because MIRS from litterbag experiments contain information about the relative abundance and interactions of many molecular structures <xref ref-type="bibr" rid="bib1.bibx61" id="paren.15"/> which change in abundance during decomposition and differ between plant species <xref ref-type="bibr" rid="bib1.bibx2 bib1.bibx19 bib1.bibx22 bib1.bibx76" id="paren.16"><named-content content-type="pre">e.g.</named-content></xref>. In contrast to other decomposition indicators that use simple formulas and no training data, such as C<inline-formula><mml:math id="M34" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>N or humification indices, using a statistical model and undecomposed litter from various species as reference should avoid confounding differences in the chemistry of undecomposed litter with differences in chemistry due to decomposition. In contrast to <inline-formula><mml:math id="M35" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>ARM</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, no knowledge of initial states is required because <inline-formula><mml:math id="M36" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is predicted only with information from the decomposed sample. Previous studies used MIRS to predict various peat properties <xref ref-type="bibr" rid="bib1.bibx4 bib1.bibx19" id="paren.17"><named-content content-type="pre">e.g.</named-content></xref>, but, to our knowledge, not <inline-formula><mml:math id="M37" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>.</p>
      <p id="d2e535">Peat samples can be much more complex than samples used in typical litterbag experiments because peat can be a mixture of multiple components: litter of different plant species and organs, possibly with different degree of decomposition and different changes of chemical components (e.g. cellulose, lignin, lipids) during decomposition, microbial bio- and necromass, and minerals. Therefore, it will be important not only to evaluate <inline-formula><mml:math id="M38" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with homogeneous litter data, but also to evaluate <inline-formula><mml:math id="M39" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for mixtures of litter types similar to peat samples. To generate a diverse set of mixtures, one can add spectra of litterbag samples multiplied by scale factors. According to the Beer–Lambert law and with constant path length, these scale factors are the mass fractions of the components <xref ref-type="bibr" rid="bib1.bibx61" id="paren.18"/> because MIRS intensities are proportional to the relative abundance of molecular structures and the relative abundance of a molecular structure is a weighted average of the relative abundances of the molecular structure of all components, where weights are the components' mass fractions. Also <inline-formula><mml:math id="M40" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> can be calculated for these mixtures from <inline-formula><mml:math id="M41" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of the individual components and the initial litter masses, which allows us to test <inline-formula><mml:math id="M42" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for peat samples.</p>
      <p id="d2e589">Theoretical considerations suggest that <inline-formula><mml:math id="M43" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> will underestimate <inline-formula><mml:math id="M44" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for mixtures of litter types: whereas both MIRS intensities and <inline-formula><mml:math id="M45" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> are weighted averages of the components' values, the weights are not the same. For MIRS intensities, the weights are the mass fractions of the components in the sample, as mentioned above, whereas for <inline-formula><mml:math id="M46" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, the weights are the mass fractions of the components in the undecomposed sample. This difference also propagates to <inline-formula><mml:math id="M47" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> predictions:

              <disp-formula specific-use="align" content-type="numbered"><mml:math id="M48" display="block"><mml:mtable displaystyle="true"><mml:mtr><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:msup><mml:mi>f</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mrow><mml:mi>k</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>K</mml:mi></mml:munderover><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mrow><mml:mi>w</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>W</mml:mi></mml:munderover><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi>w</mml:mi></mml:msub><mml:mi>h</mml:mi><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi>I</mml:mi><mml:mrow><mml:mi>k</mml:mi><mml:mo>,</mml:mo><mml:mi>w</mml:mi></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mfenced></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mlabeledtr id="Ch1.E1"><mml:mtd><mml:mtext>1</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">γ</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:mo>-</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>=</mml:mo><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mrow><mml:mi>k</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>K</mml:mi></mml:munderover><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><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>

        where <inline-formula><mml:math id="M49" display="inline"><mml:mrow><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is the time when the sample was undecomposed, <inline-formula><mml:math id="M50" display="inline"><mml:mi>t</mml:mi></mml:math></inline-formula> is some time point later than <inline-formula><mml:math id="M51" display="inline"><mml:mrow><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M52" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula>, and <inline-formula><mml:math id="M53" display="inline"><mml:mi>w</mml:mi></mml:math></inline-formula> are indices for the component and wavenumber, <inline-formula><mml:math id="M54" display="inline"><mml:mrow><mml:msub><mml:mi>I</mml:mi><mml:mrow><mml:mi>k</mml:mi><mml:mo>,</mml:mo><mml:mi>w</mml:mi></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is the MIRS intensity at wavenumber <inline-formula><mml:math id="M55" display="inline"><mml:mi>w</mml:mi></mml:math></inline-formula> in component <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:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</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="M58" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> are the mass and initial mass of component <inline-formula><mml:math id="M59" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math id="M60" display="inline"><mml:mrow><mml:mi>m</mml:mi><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="M61" display="inline"><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> are the mass and initial mass of the mixture, <inline-formula><mml:math id="M62" display="inline"><mml:mrow><mml:msup><mml:mi>f</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> is the inverse link function of the prediction model for <inline-formula><mml:math id="M63" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, where we assume that the model is linear on the link scale with intercept <inline-formula><mml:math id="M64" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and coefficients <inline-formula><mml:math id="M65" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi>w</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> for each wavenumber, and <inline-formula><mml:math id="M66" display="inline"><mml:mi>h</mml:mi></mml:math></inline-formula> is a transformation of raw intensity values due to spectral preprocessing (for example standard normal variate (SNV) normalization and <inline-formula><mml:math id="M67" display="inline"><mml:mi>z</mml:mi></mml:math></inline-formula>-transformation of predictors). Therefore, more decomposed components have a smaller weight for <inline-formula><mml:math id="M68" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> than for <inline-formula><mml:math id="M69" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, suggesting that <inline-formula><mml:math id="M70" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>&lt;</mml:mo><mml:mi mathvariant="italic">γ</mml:mi></mml:mrow></mml:math></inline-formula>, unless all components have the same <inline-formula><mml:math id="M71" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> or the sample consists only of one component.</p>
      <p id="d2e1111">If the bias is not negligible, alternative strategies to accurately estimate <inline-formula><mml:math id="M72" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> also for peat samples to the direct measurement of <inline-formula><mml:math id="M73" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> with <inline-formula><mml:math id="M74" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> need to be developed. When <inline-formula><mml:math id="M75" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> accurately estimates <inline-formula><mml:math id="M76" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for individual litter types and <inline-formula><mml:math id="M77" display="inline"><mml:mi>h</mml:mi></mml:math></inline-formula> is a function such that <inline-formula><mml:math id="M78" display="inline"><mml:mrow><mml:mi>h</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>I</mml:mi><mml:mrow><mml:mi>k</mml:mi><mml:mo>,</mml:mo><mml:mi>w</mml:mi></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>h</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>I</mml:mi><mml:mrow><mml:mi>k</mml:mi><mml:mo>,</mml:mo><mml:mi>w</mml:mi></mml:mrow></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>)</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:math></inline-formula>, then it should be possible to estimate <inline-formula><mml:math id="M79" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for mixtures from <inline-formula><mml:math id="M80" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> for each component <inline-formula><mml:math id="M81" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> as:

              <disp-formula id="Ch1.E2" content-type="numbered"><label>2</label><mml:math id="M82" display="block"><mml:mstyle class="stylechange" displaystyle="true"/><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:msup><mml:mi>f</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mrow><mml:mi>k</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow><mml:mi>K</mml:mi></mml:munderover><mml:mo>(</mml:mo><mml:mi>f</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><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 mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mfenced></mml:mrow></mml:math></disp-formula></p>
      <p id="d2e1394">At first glance, it does not seem helpful to estimate <inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> from <inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> to estimate <inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, but many peat samples consist of one or few dominant components which then also dominate the value of <inline-formula><mml:math id="M86" display="inline"><mml:mrow><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. Using Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>) in a mixing model <xref ref-type="bibr" rid="bib1.bibx23" id="paren.19"><named-content content-type="pre">e.g.</named-content></xref> then allows us to estimate <inline-formula><mml:math id="M87" display="inline"><mml:mrow><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> from <inline-formula><mml:math id="M88" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and we even get estimates for <inline-formula><mml:math id="M89" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> for free (Fig. <xref ref-type="fig" rid="F1"/>). Such a mixing model works when we know the mass fraction of each component (<inline-formula><mml:math id="M90" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>). To analyze existing data, we suggest to approximate <inline-formula><mml:math id="M91" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> from the volume fractions in macrofossil analysis, as is also assumed in current peatland models <xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx79 bib1.bibx50" id="paren.20"><named-content content-type="pre">e.g.</named-content></xref>. The same strategy also works when integrating <inline-formula><mml:math id="M92" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> into peatland models. We note that theory also suggests similar biases for other decomposition indicators (that measure a property of the decomposing organic material), were these indicators used to estimate <inline-formula><mml:math id="M93" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. Therefore, the bias is a general limitation when we attempt to estimate <inline-formula><mml:math id="M94" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>.</p>

      <fig id="F1"><label>Figure 1</label><caption><p id="d2e1605">Two analytical and data analysis workflows to estimate the degree of decomposition (<inline-formula><mml:math id="M95" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>) of a peat sample. Workflow (1) predicts <inline-formula><mml:math id="M96" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> of the peat sample from a mid-infrared spectrum (MIRS) measured on a bulk peat sample. The <inline-formula><mml:math id="M97" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> estimate and macrofossil volume fraction estimates from a macrofossil analysis are input to a mixing model that estimates <inline-formula><mml:math id="M98" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of the peat sample as average of <inline-formula><mml:math id="M99" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> for all macrofossil types (components). Workflow (2) first splits the peat sample into individual components (e.g. macrofossil types) and then measures a MIRS and the mass of each component. The prediction of <inline-formula><mml:math id="M100" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for a component equals <inline-formula><mml:math id="M101" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of this component. <inline-formula><mml:math id="M102" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of the peat sample can be computed as weighted average using Eq. (<xref ref-type="disp-formula" rid="Ch1.E1"/>) (no mixing model is needed). Workflow (2) is preferred because errors from macrofossil analysis and from not knowing the initial mass of each component <inline-formula><mml:math id="M103" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>) are avoided. Workflow (1) is applicable to available bulk measurements. See the text for details.</p></caption>
        <graphic xlink:href="https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026-f01.png"/>

      </fig>

      <p id="d2e1716">Here, we address the problems of estimating <inline-formula><mml:math id="M105" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of individual litter types and peat, and the question whether it is possible to estimate <inline-formula><mml:math id="M106" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of individual litter samples and of peat with <inline-formula><mml:math id="M107" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>. In this context, our aims are:
<list list-type="order"><list-item>
      <p id="d2e1748">To develop a novel decomposition indicator, <inline-formula><mml:math id="M108" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, which we define as <inline-formula><mml:math id="M109" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, as measured in litterbag experiments, predicted from MIRS with a spectral prediction model.</p></list-item><list-item>
      <p id="d2e1770">To evaluate how well the developed models predict <inline-formula><mml:math id="M110" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for peat samples as mixtures of litter types from (1) different species, (2) with different degree of decomposition, and (3) with admixtures of silicate minerals.</p></list-item><list-item>
      <p id="d2e1781">To develop a simple mixing model that allows to estimate <inline-formula><mml:math id="M111" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of peat samples from bulk measurements and macrofossil volume fractions.</p></list-item><list-item>
      <p id="d2e1792">To illustrate and discuss how <inline-formula><mml:math id="M112" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> can be used to address open questions in peatland research (including the relation between saturated hydraulic conductivity and <inline-formula><mml:math id="M113" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>), to improve process models, to reconstruct past NPP, and to define site-specific references for <inline-formula><mml:math id="M114" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and NPP for peatland restoration.</p></list-item></list></p>
      <p id="d2e1820">To this end, we collected available data from undecomposed litter and litterbag experiments for which MIRS and measurements of some commonly used decomposition indicators are available. This enabled us to compute beta regression models that predict <inline-formula><mml:math id="M115" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> from MIRS. Several models are computed because MIRS can be preprocessed in different ways and this may lead to differences in prediction errors and robustness. We evaluated the models on individual litter types using cross-validation and residual plots vs. N contents, a known confounder of predictions from MIRS models <xref ref-type="bibr" rid="bib1.bibx68" id="paren.21"><named-content content-type="pre">e.g.</named-content></xref>. To evaluate applicability to peat samples, we apply the models to three sets of mixed spectra: mixtures of undecomposed material from different species, mixtures of material from different species and with different degree of decomposition, and mixtures of litter with a silicate-rich peat sample. Here, we test whether <inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> underestimates <inline-formula><mml:math id="M117" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for mixtures of litter types as predicted by the theoretical model in Eqs. (<xref ref-type="disp-formula" rid="Ch1.E1"/>) and (<xref ref-type="disp-formula" rid="Ch1.E2"/>). Based on this analysis, we develop strategies to avoid this bias and show how <inline-formula><mml:math id="M118" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> can be used to estimate <inline-formula><mml:math id="M119" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and reconstruct past NPP for peat cores.</p>
      <p id="d2e1876">By developing and evaluating models that predict <inline-formula><mml:math id="M120" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of litter from MIRS, we contribute to the development of a method that allows to accurately estimate <inline-formula><mml:math id="M121" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of peat, therefore to better understand decomposition processes, reconstruct past NPP, and improve process models. This will contribute to a better understanding of peat accumulation processes, the definition of ecological baselines, and prediction of future peatland dynamics.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Methods</title>
<sec id="Ch1.S2.SS1">
  <label>2.1</label><title>Training data</title>
      <p id="d2e1909">For our analyses, we used the following litterbag data: <italic>Sphagnum capillifolium</italic> (capitulum and first 5 <inline-formula><mml:math id="M122" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">cm</mml:mi></mml:mrow></mml:math></inline-formula> of the stem; 20 samples) and <italic>Typha latifolia</italic> (leaves; 20 samples) samples incubated in bog peat and pools (oxic and anoxic conditions) in Canada for 808 <inline-formula><mml:math id="M123" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">d</mml:mi></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx2 bib1.bibx3" id="paren.22"/>, and <italic>Phragmites australis</italic> (leaves and rhizomes; 36 samples) grown under different nutrient availability and incubated under anoxic conditions in peat with different nutrient availability for 75 <inline-formula><mml:math id="M124" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">d</mml:mi></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx53 bib1.bibx54 bib1.bibx55" id="paren.23"/>. In both cases, MIRS were measured for the undecomposed litter and at the end of the incubation period. In addition, we used undecomposed litter samples (some collected under natural conditions, some grown in laboratory experiments with different nutrient availability) of <italic>Astelia pumila</italic>, <italic>Aulacomnium palustre</italic>, <italic>Betula populifolia</italic>, <italic>Calluna vulgaris</italic>, <italic>Chamedaphne calyculata</italic>, <italic>Donatia fascicularis</italic>, <italic>Empetrum nigrum</italic>, <italic>Empetrum rubrum</italic>, <italic>Eriophorum</italic> sp., <italic>Eriophorum angustifolium</italic>, <italic>Eriophorum vaginatum</italic>, <italic>Gaultheria antarctica</italic>, <italic>Isolepis setacea</italic>, <italic>Juncus effusus</italic>, <italic>Kalmia angustifolia</italic>, <italic>Larix laricina</italic>, <italic>Lepidothamnus fonkii</italic>, <italic>Polytrichum strictum</italic>, <italic>Rhododendron groenlandicum</italic>, <italic>Sphagnum</italic> sp., <italic>Sphagnum capillifolium</italic>, <italic>Sphagnum fallax</italic>, <italic>Sphagnum magellanicum</italic>, <italic>Sphagnum rubellum</italic>, <italic>Tracheophyta</italic>, <italic>Vaccinium myrtilloides</italic>, <italic>Vaccinium myrtillus</italic>, <italic>Vaccinium oxycoccos</italic>, <italic>Vaccinium uliginosum</italic>, and <italic>Vaccinium vitis-idaea</italic> (<xref ref-type="bibr" rid="bib1.bibx1 bib1.bibx39 bib1.bibx41 bib1.bibx16 bib1.bibx88" id="altparen.24"/>; R. Anzenhofer, unpublished; A. Hömberg, unpublished; S. Wagner, unpublished) from the Peatland Mid-Infrared Database <xref ref-type="bibr" rid="bib1.bibx70 bib1.bibx74" id="paren.25"/>. For undecomposed litter samples, we assumed a degree of decomposition of 0 <inline-formula><mml:math id="M125" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>. In total, 169 litter samples were available for model training. All MIRS used in this study are measured in transmission mode on Fourier-transform infrared spectrometers (FTIR) as milled samples mixed with potassium bromide into transparent pellets. MIRS were measured on different devices (Cary 660 FTIR spectrometer (Agilent, Santa Clara, CA, USA), Bruker Vector 22 FTIR spectrometer (Bruker Optik, Ettlingen, Germany), Cary 600 FTIR spectrometer (Agilent, Santa Clara, CA, USA), Varian 660 FTIR spectrometer (Agilent, Palo Alto, USA), Cary 670 FTIR spectrometer (Agilent, Santa Clara, CA, USA), and Shimadzu IRTracer-100 spectrophotometer, equipped with a DLaTGS (deuterated L-alaninedoped triglycine sulfate) detector). Different devices may lead to differences in spectra not related to <inline-formula><mml:math id="M126" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> which may lead to larger prediction errors than when all MIRS were measured with the same device.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <label>2.2</label><title>Peat data</title>
      <p id="d2e2078">To evaluate the models and to illustrate the application of <inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, we used bog peat core measurements derived from the Peatland Mid-Infrared Database: a core from the peatland Odersprungmoor (OD2) <xref ref-type="bibr" rid="bib1.bibx30" id="paren.26"/>, a core from the peatland Martinskapelle (MK1) <xref ref-type="bibr" rid="bib1.bibx31" id="paren.27"/>, and a core from the peatland Mohoş (MH1) <xref ref-type="bibr" rid="bib1.bibx24" id="paren.28"/>. Macrofossil volume fractions from these cores were used to estimate the mass fractions of individual litter components in the peat samples and average water table depth reconstructed from testate amoebae (TA-WTD) were used to relate estimated <inline-formula><mml:math id="M128" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and NPP to changes in WTD. Age-depth models were estimated with <inline-formula><mml:math id="M129" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> dates using rbacon <xref ref-type="bibr" rid="bib1.bibx13" id="paren.29"/> (supporting Sect. S1 in the Supplement). In addition, we also used data from three ombrotrophic Patagonian peat cores from <xref ref-type="bibr" rid="bib1.bibx17" id="text.30"/> and two bog peat cores with highly degraded drainage layers from the Venner Moor to evaluate prediction domains of the models (see Sect. <xref ref-type="sec" rid="Ch1.S2.SS4.SSS2"/>).</p>
</sec>
<sec id="Ch1.S2.SS3">
  <label>2.3</label><title>Prediction model development</title>
      <p id="d2e2137">We used beta regression models to predict <inline-formula><mml:math id="M130" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> from intensities in preprocessed MIRS. To harmonize the spectra, we interpolated them to unit wavenumber resolution and clipped them to the range 600–4000 <inline-formula><mml:math id="M131" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>. Depending on the variable and properties of the MIRS, different preprocessing steps may maximize predictive performance. Therefore, we computed models with different preprocessing steps in addition to the harmonization: (1) Baseline correction, signal normal variate (SNV) (model 1), (2) First derivative spectra, SNV (model 2), (3) Second derivative spectra, SNV (model 3). After that, spectra were binned (bin width 10 <inline-formula><mml:math id="M132" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) to reduce the number of predictors and reduce correlation between predictors, and all predictors were <inline-formula><mml:math id="M133" display="inline"><mml:mi>z</mml:mi></mml:math></inline-formula>-transformed across all spectra. All preprocessing steps were performed with the ir package <xref ref-type="bibr" rid="bib1.bibx64" id="paren.31"/>. Baseline correction was done with an automated convex hull procedure <xref ref-type="bibr" rid="bib1.bibx8" id="paren.32"/>. Spectra of some undecomposed litter samples have artefacts from <inline-formula><mml:math id="M134" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, as indicated by peaks around 2360 <inline-formula><mml:math id="M135" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx85" id="paren.33"/>. To avoid that these peaks have an effect on the normalization or models, we linearly interpolated intensities between 2300–2380 <inline-formula><mml:math id="M136" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> and excluded variables from this range from the models. <inline-formula><mml:math id="M137" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> also produces peaks around 670 and 3580–3780 <inline-formula><mml:math id="M138" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, but we did not correct these because they overlap with peaks from organic matter and are smaller than the peaks between 2300–2380 <inline-formula><mml:math id="M139" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx85" id="paren.34"/>.</p>
      <p id="d2e2274">Beta regression models were computed with brms <xref ref-type="bibr" rid="bib1.bibx18" id="paren.35"/>, using a logit link function, assuming a constant shape parameter, using a normal prior for the intercept, and regularized horseshoe priors <xref ref-type="bibr" rid="bib1.bibx47 bib1.bibx48" id="paren.36"/> for the slopes (for each predictor variable). The regularized horseshoe prior shrinks coefficients to zero except where they are strongly related to the response variable, conditional on other predictors. To reduce overfitting, we defined a large amount of shrinkage, by assuming that 5 of the 321 predictor variables have non-zero coefficients <xref ref-type="bibr" rid="bib1.bibx48" id="paren.37"/>. Bayesian inference was done using Markov Chain Monte Carlo (MCMC) sampling with Stan <xref ref-type="bibr" rid="bib1.bibx60" id="paren.38"/>, using 2000 warmup iterations and 2000 sampling iterations. Across all models, the maximum Monte Carlo standard error <xref ref-type="bibr" rid="bib1.bibx81" id="paren.39"/> for the degree of decomposition predicted for the training data and all analyzed peat samples was 1.1 <inline-formula><mml:math id="M140" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> for the mean, 0.5 <inline-formula><mml:math id="M141" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> (for standard deviations), and 4 <inline-formula><mml:math id="M142" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> (for lower and upper 95 <inline-formula><mml:math id="M143" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> prediction interval boundaries). No model had divergent transitions and the largest rank-normalized <inline-formula><mml:math id="M144" display="inline"><mml:mover accent="true"><mml:mi>R</mml:mi><mml:mo stretchy="false" mathvariant="normal">^</mml:mo></mml:mover></mml:math></inline-formula> for model parameters was 1.01, indicating convergence of the chains <xref ref-type="bibr" rid="bib1.bibx81" id="paren.40"/>.</p>
</sec>
<sec id="Ch1.S2.SS4">
  <label>2.4</label><title>Model evaluation for litter samples</title>
<sec id="Ch1.S2.SS4.SSS1">
  <label>2.4.1</label><title>Prediction errors for individual litter types</title>
      <p id="d2e2353">We estimated the predictive accuracy of the models with 10-fold cross-validation (CV). CV folds were defined in two ways to evaluate predictive performance for two scenarios. In the first scenario, we used stratified CV, where each observation is assigned to a categorical variable and observations are split into the 10 folds while approximately preserving relative category frequencies. Each observation was assigned to a category based on the study and species, or, for samples from <xref ref-type="bibr" rid="bib1.bibx53" id="text.41"/>, based on the study, species, and the site where the litter was grown (to balance occurrence of rhizome litter with different nutrient contents). This procedure approximates a test of the models with samples similar to the training data, as far as this is possible with our small and heterogeneous dataset.</p>
      <p id="d2e2359">In the second scenario, we used grouped CV, where each observation is assigned to a categorical variable and observations for the same categorical variable all are assigned to the same fold. The categorical variable was the same as for the stratified CV. This estimates predictive performance for novel litter types that are not part of the training data, for example the only litterbag data with <italic>Sphagnum</italic> litter is from <xref ref-type="bibr" rid="bib1.bibx2" id="text.42"/>, and therefore in this scenario a model not trained on decomposed <italic>Sphagnum</italic> litter predicts the degree of decomposition for decomposed <italic>Sphagnum</italic> litter. The procedure also implies that some folds only contain undecomposed litter because there are fewer categories for litterbag data than CV-folds. The purpose of this second scenario is to test model robustness for novel litter types.</p>
      <p id="d2e2374">To compare models, we used the expected log predictive density (ELPD) computed on observations held out during CV. Model evaluation was performed with the loo package <xref ref-type="bibr" rid="bib1.bibx80" id="paren.43"/>. Following rules of thumb <xref ref-type="bibr" rid="bib1.bibx59" id="paren.44"/>, we assumed models to have equivalent predictive performance (according to the capability of our evaluation) when the difference of their ELPD (<inline-formula><mml:math id="M145" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD) is smaller than 4, and otherwise when <inline-formula><mml:math id="M146" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD is larger than two times its standard error (using a normal approximation for <inline-formula><mml:math id="M147" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD). To give an easier to interpret performance metric, we also computed the root mean square error (RMSE).</p>
</sec>
<sec id="Ch1.S2.SS4.SSS2">
  <label>2.4.2</label><title>Prediction domain coverage</title>
      <p id="d2e2412">We analyzed what fraction of the analyzed peat samples is within the prediction domain of the models. The prediction domain of a model (based on <xref ref-type="bibr" rid="bib1.bibx84" id="altparen.45"/>, defined in <xref ref-type="bibr" rid="bib1.bibx69" id="altparen.46"/>) is the range of the predictor variables covered by the training data. A sample is within the prediction domain if its preprocessed spectrum is within the range for each predictor variable, otherwise it is outside the prediction domain. If a sample is outside the prediction domain, it has spectral properties that cannot be interpolated from the training data and therefore the model extrapolates when making predictions for the spectra. In particular with models that overfit, this may lead to larger prediction errors than fitting errors for the training data.</p>
</sec>
<sec id="Ch1.S2.SS4.SSS3">
  <label>2.4.3</label><title>Relations of model residuals to N content</title>
      <p id="d2e2429">We analyzed whether residuals are related to the nitrogen (N) content as proxy for proteins because it is known that protein content differs between species and increases during decomposition <xref ref-type="bibr" rid="bib1.bibx55 bib1.bibx57 bib1.bibx35 bib1.bibx12" id="paren.47"/>, and that proteins, despite their comparatively small amount in peat, are a main control of the height and shape of peaks that are also caused by aromatics <xref ref-type="bibr" rid="bib1.bibx61" id="paren.48"/>. Thus, if one considers that the training data contains decomposed litter only from three species, the fit of the models may be confounded by proteins and this may bias predictions, especially under extrapolation. For 17 of the litter samples, no N measurements were available. For these samples, we predicted N contents from MIRS using prediction models from the irpeatmodels package <xref ref-type="bibr" rid="bib1.bibx65 bib1.bibx69" id="paren.49"/>. MIRS-predicted N contents are labelled <inline-formula><mml:math id="M148" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">MIRS</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and we indicate whether predictions are within the training prediction domain of the model <xref ref-type="bibr" rid="bib1.bibx69" id="paren.50"/>.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS5">
  <label>2.5</label><title>Model evaluation for mixtures of peat components</title>
<sec id="Ch1.S2.SS5.SSS1">
  <label>2.5.1</label><title>Admixtures of minerals</title>
      <p id="d2e2472">The impacts of minerals on the estimated degree of decomposition was evaluated by adding a scaled version of a spectrum of a peat sample from the Peatland Mid-Infrared Database <xref ref-type="bibr" rid="bib1.bibx25 bib1.bibx26" id="paren.51"/> with large mineral content (0.47 <inline-formula><mml:math id="M149" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, computed from loss on ignition; based on the mid-infrared spectrum (Fig. S6 in the Supplement), many of the minerals are silicates <xref ref-type="bibr" rid="bib1.bibx61 bib1.bibx46" id="altparen.52"/>) to selected spectra from the training data from different taxa and with different <inline-formula><mml:math id="M150" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. A range of scaling factors from absence of silicates to a clear dominance of silicates was chosen and we predicted <inline-formula><mml:math id="M151" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for each spectrum created this way. For the same samples from the training data, we evaluated the impact of adding increasing amounts of a very decomposed sample (based on <inline-formula><mml:math id="M152" display="inline"><mml:mrow><mml:msub><mml:mtext>HI</mml:mtext><mml:mrow><mml:mn mathvariant="normal">1630</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1090</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>, peat structure, C content, and degree of decomposition predicted by all models).</p>
</sec>
<sec id="Ch1.S2.SS5.SSS2">
  <label>2.5.2</label><title>Mixtures of undecomposed and decomposed litter</title>
      <p id="d2e2537">To evaluate how robust the models are for mixtures of litter from different taxa and with different <inline-formula><mml:math id="M153" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, we created pairwise mixtures from two sets of spectra. The first set consisted of randomly selected undecomposed litter samples from 15 taxa and the two most decomposed samples per taxon (where available). The spectra in this set were scaled in the range 0.001–1000. The second set consisted of the two most decomposed samples and the least decomposed sample per taxon, which are not already in the first set. All pairwise mixtures of the spectra from the first and second set were created and <inline-formula><mml:math id="M154" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> predicted with all three models. Values of <inline-formula><mml:math id="M155" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> were computed with Eq. (<xref ref-type="disp-formula" rid="Ch1.E1"/>). The value of <inline-formula><mml:math id="M156" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is measured in the litterbag experiments, the value of <inline-formula><mml:math id="M157" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> is computed by assuming that the scale factors correspond to masses (as outlined in the Introduction) as: <inline-formula><mml:math id="M158" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. Values of <inline-formula><mml:math id="M159" display="inline"><mml:mrow><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> are computed as sum of the scale factors of the components. We then used <inline-formula><mml:math id="M160" display="inline"><mml:mrow><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> measured for each component and Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>) to estimate <inline-formula><mml:math id="M161" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> to test whether this theoretical model can reproduce <inline-formula><mml:math id="M162" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for the mixtures, irrespective of the litter type (see also workflow (2) in Fig. <xref ref-type="fig" rid="F1"/>).</p>
      <p id="d2e2715">To evaluate in more detail how robust the models are for mixtures of undecomposed litter, we selected one sample per taxon from the undecomposed litter samples and created all pairwise mixtures with equal amounts of both components. It was tested whether predictions of the models for these mixtures match the expected value for <inline-formula><mml:math id="M163" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of 0 <inline-formula><mml:math id="M164" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS6">
  <label>2.6</label><title>Estimation of <inline-formula><mml:math id="M165" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for peat cores from bulk measurements of <inline-formula><mml:math id="M166" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and reconstruction of past NPP</title>
      <p id="d2e2776">We developed a simple Bayesian mixing model based on Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>) that estimates <inline-formula><mml:math id="M167" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> for all components in a peat sample from bulk measurements of <inline-formula><mml:math id="M168" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>t</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (predicted by any of the three models) and the mass fractions of the components:

                <disp-formula specific-use="align" content-type="numbered"><mml:math id="M169" display="block"><mml:mtable displaystyle="true"><mml:mtr><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>∼</mml:mo><mml:mtext>beta</mml:mtext><mml:mo>(</mml:mo><mml:msub><mml:mi mathvariant="italic">μ</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:msub><mml:msub><mml:mi mathvariant="italic">ϕ</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:msub><mml:mo>,</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="italic">μ</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:msub><mml:mo>)</mml:mo><mml:msub><mml:mi mathvariant="italic">ϕ</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:msub><mml:mi mathvariant="italic">μ</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:msub><mml:mo>∼</mml:mo><mml:mtext>beta</mml:mtext><mml:mo>(</mml:mo><mml:mi mathvariant="italic">μ</mml:mi><mml:mi mathvariant="italic">ϕ</mml:mi><mml:mo>,</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mi mathvariant="italic">μ</mml:mi><mml:mo>)</mml:mo><mml:mi mathvariant="italic">ϕ</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi mathvariant="italic">μ</mml:mi><mml:mo>=</mml:mo><mml:msup><mml:mtext>logit</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:munderover><mml:mo movablelimits="false">∑</mml:mo><mml:mi>k</mml:mi><mml:mi>K</mml:mi></mml:munderover><mml:mo>(</mml:mo><mml:mtext>logit</mml:mtext><mml:mo>(</mml:mo><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>)</mml:mo><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow><mml:mi>m</mml:mi></mml:mfrac></mml:mstyle></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mi mathvariant="italic">ϕ</mml:mi><mml:mo>∼</mml:mo><mml:mtext>gamma</mml:mtext><mml:mo>(</mml:mo><mml:msub><mml:mi mathvariant="italic">α</mml:mi><mml:mi mathvariant="italic">ϕ</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">ϕ</mml:mi></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>∼</mml:mo><mml:mtext>beta</mml:mtext><mml:mo>(</mml:mo><mml:msub><mml:mi mathvariant="italic">α</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:msub><mml:mo>,</mml:mo><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mlabeledtr id="Ch1.E3"><mml:mtd><mml:mtext>3</mml:mtext></mml:mtd><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>∼</mml:mo><mml:mtext>normal</mml:mtext><mml:mo>(</mml:mo><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mrow><mml:msub><mml:mn mathvariant="normal">0</mml:mn><mml:mi mathvariant="italic">μ</mml:mi></mml:msub></mml:mrow></mml:msub><mml:mo>,</mml:mo><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mrow><mml:msub><mml:mn mathvariant="normal">0</mml:mn><mml:mi mathvariant="italic">σ</mml:mi></mml:msub></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

          where the third line is the same as Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>), the first line is a measurement error model to consider prediction errors in <inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (here, we approximate errors of the prediction model with a beta distribution with scale parameter <inline-formula><mml:math id="M171" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ϕ</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> computed from the average prediction error of the respective model), <inline-formula><mml:math id="M172" display="inline"><mml:mi mathvariant="italic">μ</mml:mi></mml:math></inline-formula> is the estimated true value of <inline-formula><mml:math id="M173" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (without measurement errors), <inline-formula><mml:math id="M174" display="inline"><mml:mi mathvariant="italic">ϕ</mml:mi></mml:math></inline-formula> is the scale parameter of the beta distribution (with a gamma prior with shape and rate parameters <inline-formula><mml:math id="M175" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">α</mml:mi><mml:mi mathvariant="italic">ϕ</mml:mi></mml:msub><mml:mo>,</mml:mo><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mi mathvariant="italic">ϕ</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>), and <inline-formula><mml:math id="M176" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> of component <inline-formula><mml:math id="M177" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> is modeled with a beta distribution with shape and rate parameters <inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">α</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M179" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>. As outlined in the Introduction, linking this model to peat core data can be done with bulk measurements for <inline-formula><mml:math id="M180" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and by assuming that <inline-formula><mml:math id="M181" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>k</mml:mi></mml:msub><mml:mo>/</mml:mo><mml:mi>m</mml:mi></mml:mrow></mml:math></inline-formula> equals the macrofossil volume fractions of the litter components (workflow (1) in Fig. <xref ref-type="fig" rid="F1"/>). For individual litter types, the mixing model will only yield correct estimates for <inline-formula><mml:math id="M182" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> when they have a relatively large mass fraction because <inline-formula><mml:math id="M183" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is not sensitive to <inline-formula><mml:math id="M184" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> if component <inline-formula><mml:math id="M185" display="inline"><mml:mi>k</mml:mi></mml:math></inline-formula> has only a small mass fraction. To consider this error source, we used a <inline-formula><mml:math id="M186" display="inline"><mml:mrow><mml:mtext>beta</mml:mtext><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>,</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> prior for <inline-formula><mml:math id="M187" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, which gives uniform weights to all possible values. Unless the sample consists of many components, the inability to correctly estimate <inline-formula><mml:math id="M188" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> for components with small mass fraction in the sample has only a small effect on <inline-formula><mml:math id="M189" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and an even smaller effect on the reconstructed NPP. We expect large errors not accounted for by the mixing model only when some initially dominant component is completely or nearly completely decomposed and therefore not detectable.</p>
      <p id="d2e3343">We applied this model to the three cores, OD2, MK1, and MH1 described in Sect. <xref ref-type="sec" rid="Ch1.S2.SS2"/> to estimate <inline-formula><mml:math id="M190" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> of all <inline-formula><mml:math id="M191" display="inline"><mml:mi>K</mml:mi></mml:math></inline-formula> litter components and <inline-formula><mml:math id="M192" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of the peat samples. With these estimates for <inline-formula><mml:math id="M193" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mi>k</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, bulk densities estimated from MIRS <xref ref-type="bibr" rid="bib1.bibx69 bib1.bibx65" id="paren.53"/>, and age-depth models for each core, we could then estimate the initial mass of each layer, which divided by the time range of aboveground litter formation in each layer without roots equals the aboveground NPP. Reconstruction of belowground NPP is only possible with peatland models. If there is a large fraction of roots in a sample, a large fraction of the initial mass may have been added to the layer after its initial formation by aboveground litter. In presence of roots, we therefore call our estimate the initial mass accumulation rate. We developed an R package that allows to estimate the mixing model for own data <xref ref-type="bibr" rid="bib1.bibx66" id="paren.54"/>.</p>
      <p id="d2e3391">Our analysis considers errors in estimates for <inline-formula><mml:math id="M194" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, bulk density, peat ages, and <inline-formula><mml:math id="M195" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. Errors from <inline-formula><mml:math id="M196" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, bulk density predicted from MIRS and peat ages are propagated to NPP estimates by computing NPP with individual draws from the posterior distributions of the respective Bayesian models. Errors for <inline-formula><mml:math id="M197" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M198" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> are considered by using prior distributions within the mixing model with parameters chosen based on the prediction models for <inline-formula><mml:math id="M199" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>.</p>
      <p id="d2e3458">Clearly, prediction of bulk density and saturated hydraulic conductivity from MIRS introduces larger errors in our analysis than necessary. We used predictions because we do not have access to peat samples with estimates for peat ages, macrofossils, bulk density, and saturated hydraulic conductivity. We present these analyses as illustrations for the suggested approach but severe tests may require more accurate estimates and measurements than are currently available. Errors can also be reduced further by measuring mass fractions of macrofossils and by measuring MIRS on individual macrofossils than on bulk samples (workflow (2) in Fig. <xref ref-type="fig" rid="F1"/>).</p>
</sec>
<sec id="Ch1.S2.SS7">
  <label>2.7</label><title>Relation between saturated hydraulic conductivity and <inline-formula><mml:math id="M200" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula></title>
      <p id="d2e3478">Using the estimated <inline-formula><mml:math id="M201" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for the peat samples and saturated hydraulic conductivity (<inline-formula><mml:math id="M202" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) estimated from MIRS <xref ref-type="bibr" rid="bib1.bibx65 bib1.bibx69" id="paren.55"/>, we tested whether <inline-formula><mml:math id="M203" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M204" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> relations hypothesized in previous studies agree with <inline-formula><mml:math id="M205" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M206" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for our peat cores. The hypothesized relations are: <list list-type="order"><list-item>
      <p id="d2e3541">An assumed sigmoidal relation as used in the Holocene Peatland Model (corrected versions of Eqs. 10 and 15 in <xref ref-type="bibr" rid="bib1.bibx29" id="altparen.56"/>; corrected versions are available from the supporting info to <xref ref-type="bibr" rid="bib1.bibx78" id="altparen.57"/>, <inline-formula><mml:math id="M207" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> in <inline-formula><mml:math id="M208" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">cm</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">min</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, according to <xref ref-type="bibr" rid="bib1.bibx44" id="altparen.58"/>):<disp-formula specific-use="align" content-type="numbered"><mml:math id="M209" display="block"><mml:mtable displaystyle="true"><mml:mtr><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">150</mml:mn><mml:mn mathvariant="normal">70</mml:mn></mml:mfrac></mml:mstyle><mml:mo>-</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">3</mml:mn><mml:mn mathvariant="normal">70</mml:mn></mml:mfrac></mml:mstyle><mml:mo mathsize="2.5em">(</mml:mo><mml:msub><mml:mi mathvariant="italic">ρ</mml:mi><mml:mtext>min</mml:mtext></mml:msub></mml:mrow></mml:mtd></mml:mtr><mml:mlabeledtr id="Ch1.E4"><mml:mtd><mml:mtext>4</mml:mtext></mml:mtd><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi mathvariant="italic">ρ</mml:mi><mml:mfenced close=")" open="("><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.5</mml:mn><mml:mfenced open="(" close=")"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mtext>erf</mml:mtext><mml:mfenced close=")" open="("><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>)</mml:mo><mml:mo>-</mml:mo><mml:msub><mml:mi>c</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow><mml:mrow><mml:msqrt><mml:mn mathvariant="normal">2</mml:mn></mml:msqrt><mml:msub><mml:mi>c</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:mfrac></mml:mstyle></mml:mfenced></mml:mrow></mml:mfenced></mml:mrow></mml:mfenced><mml:mo mathsize="2.5em">)</mml:mo><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>where <inline-formula><mml:math id="M210" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">ρ</mml:mi><mml:mtext>min</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M211" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi mathvariant="italic">ρ</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M212" display="inline"><mml:mrow><mml:msub><mml:mi>c</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M213" display="inline"><mml:mrow><mml:msub><mml:mi>c</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> are parameters defined in <xref ref-type="bibr" rid="bib1.bibx29" id="text.59"/> and erf is the error function.</p></list-item><list-item>
      <p id="d2e3734">An assumed exponential relation <xref ref-type="bibr" rid="bib1.bibx42" id="paren.60"/> as used in the DigiBog model <xref ref-type="bibr" rid="bib1.bibx43" id="paren.61"/>:<disp-formula id="Ch1.E5" content-type="numbered"><label>5</label><mml:math id="M214" display="block"><mml:mstyle displaystyle="true" class="stylechange"/><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.001</mml:mn><mml:mi>exp⁡</mml:mi><mml:mo>(</mml:mo><mml:mn mathvariant="normal">8</mml:mn><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>)</mml:mo><mml:mo>)</mml:mo></mml:mrow></mml:math></disp-formula></p></list-item><list-item>
      <p id="d2e3779">An empirical relation that was developed with <inline-formula><mml:math id="M215" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimates derived from C<inline-formula><mml:math id="M216" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>N ratios <xref ref-type="bibr" rid="bib1.bibx44" id="paren.62"/>:<disp-formula specific-use="align" content-type="numbered"><mml:math id="M217" display="block"><mml:mtable displaystyle="true"><mml:mtr><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub><mml:mo>≈</mml:mo></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mn mathvariant="normal">1.2</mml:mn><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mn mathvariant="normal">2.6147</mml:mn><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mtext>depth</mml:mtext></mml:mrow></mml:mtd></mml:mtr><mml:mlabeledtr id="Ch1.E6"><mml:mtd><mml:mtext>6</mml:mtext></mml:mtd><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.877</mml:mn><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mtext>hollow</mml:mtext><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.020</mml:mn><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mtext>center</mml:mtext><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2.87</mml:mn><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>where depth is the mid depth of a layer, hollow is a dummy variable which is 1 when the layer is from a hollow, and center is a dummy variable which is 1 when the layer is from the center of the peatland (in our calculations, we use <inline-formula><mml:math id="M218" display="inline"><mml:mrow><mml:mtext>depth</mml:mtext><mml:mo>∈</mml:mo><mml:mo mathvariant="italic">{</mml:mo><mml:mn mathvariant="normal">0.3</mml:mn><mml:mo>,</mml:mo><mml:mn mathvariant="normal">0.5</mml:mn><mml:mo mathvariant="italic">}</mml:mo></mml:mrow></mml:math></inline-formula> m, <inline-formula><mml:math id="M219" display="inline"><mml:mrow><mml:mtext>hollow</mml:mtext><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M220" display="inline"><mml:mrow><mml:mtext>center</mml:mtext><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>).</p></list-item></list></p>
</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Results</title>
<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>Predictive performance</title>
      <p id="d2e3929">All models have a similar fit to the training data (Fig. <xref ref-type="fig" rid="F2"/>) and similar predictive performance as measured by their ELPD during CV (Table <xref ref-type="table" rid="T1"/>). Model 2 had the best average predictive accuracy (= maximum average ELPD) for the stratified CV and model 1 for the grouped CV. Using a normal approximation for <inline-formula><mml:math id="M221" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD and a two-sided significance level of 5 <inline-formula><mml:math id="M222" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>, only model 3 in the stratified CV has a detectably worse predictive accuracy than the model with best average ELPD (Table <xref ref-type="table" rid="T1"/>). Large errors of <inline-formula><mml:math id="M223" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD in the grouped CV indicate a large variability in predictive performance of the model for the different folds, as expected when testing the model with litter samples from species not included in the training data.</p>

      <fig id="F2" specific-use="star"><label>Figure 2</label><caption><p id="d2e3963">Fitted values (first column) or predictions for folds held out during CV for the two CV scenarios (second and third columns) vs. the measured <inline-formula><mml:math id="M224" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for the training data, for each model (rows). For litterbag data, different colors represent different taxa, for undecomposed litter all samples are labelled as “Other” and have the same color. For <italic>P. australis</italic> rhizomes from <xref ref-type="bibr" rid="bib1.bibx55" id="text.63"/>, we additional differentiate between initial N contents (low, medium, and high N content). Error bars are 95 <inline-formula><mml:math id="M225" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> prediction intervals. For each case, we give the average RMSE and lower and upper 95 <inline-formula><mml:math id="M226" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> confidence intervals computed from MCMC draws.</p></caption>
          <graphic xlink:href="https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026-f02.png"/>

        </fig>

<table-wrap id="T1" specific-use="star"><label>Table 1</label><caption><p id="d2e4004">Difference of expected log predictive density of all models to the best model (<inline-formula><mml:math id="M227" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD) and corresponding standard error (SE(<inline-formula><mml:math id="M228" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD)) for stratified or grouped cross-validation. In each case, the best model is at the top.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="6">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right" colsep="1"/>
     <oasis:colspec colnum="4" colname="col4" align="left"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">
         <oasis:entry namest="col1" nameend="col3" align="center" colsep="1">Stratified CV </oasis:entry>
         <oasis:entry namest="col4" nameend="col6" align="center">Grouped CV </oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1">Model</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M229" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD</oasis:entry>
         <oasis:entry colname="col3">SE(<inline-formula><mml:math id="M230" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD)</oasis:entry>
         <oasis:entry colname="col4">Model</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M231" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD</oasis:entry>
         <oasis:entry colname="col6">SE(<inline-formula><mml:math id="M232" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>ELPD)</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">2</oasis:entry>
         <oasis:entry colname="col2">0.00</oasis:entry>
         <oasis:entry colname="col3">0.00</oasis:entry>
         <oasis:entry colname="col4">1</oasis:entry>
         <oasis:entry colname="col5">0.00</oasis:entry>
         <oasis:entry colname="col6">0.00</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">1</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M233" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>17.56</oasis:entry>
         <oasis:entry colname="col3">9.24</oasis:entry>
         <oasis:entry colname="col4">2</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M234" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>33.60</oasis:entry>
         <oasis:entry colname="col6">18.38</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">3</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M235" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>34.49</oasis:entry>
         <oasis:entry colname="col3">9.55</oasis:entry>
         <oasis:entry colname="col4">3</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M236" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>91.48</oasis:entry>
         <oasis:entry colname="col6">52.05</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d2e4193">For all models, the fit to the training data is better on average (smaller average RMSE) than for predictions in the two CV scenarios (Fig. <xref ref-type="fig" rid="F2"/>), indicating that all models overfit. The two models using derivative spectra had, on average, the best fit to the training data, but worse or not much better predictive accuracy in the CV scenarios, indicating an, on average, larger overfitting risk than for model 1, which does not use derivative spectra.</p>
      <p id="d2e4198">Predictive accuracy of all models was worse for the grouped CV than for the stratified CV (Fig. <xref ref-type="fig" rid="F2"/>), as expected, because in the stratified CV models were tested with samples from similar studies and species as the data they were trained with, whereas in the grouped CV some folds contained samples from species the model was not trained with. In the grouped CV, <inline-formula><mml:math id="M237" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is underestimated by all models for decomposed <italic>T. latifolia</italic> and <italic>S. capillifolium</italic> samples from <xref ref-type="bibr" rid="bib1.bibx2" id="text.64"/>. Conversely, <inline-formula><mml:math id="M238" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is overestimated for undecomposed litter samples, with prediction errors larger than 10 <inline-formula><mml:math id="M239" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> for model 1 for <italic>C. vulgaris</italic>, and for the other two models for <italic>L. fonkii</italic>, <italic>C. vulgaris</italic>, <italic>P. australis</italic>, <italic>A. pumila</italic>, <italic>L. laricina</italic>, and <italic>C. calyculata</italic>. Model 3 has, both in the grouped and stratified CV, the largest average prediction errors for undecomposed litter (Fig. <xref ref-type="fig" rid="F2"/>).</p>
</sec>
<sec id="Ch1.S3.SS2">
  <label>3.2</label><title>Prediction domain coverage</title>
      <p id="d2e4267">A comparison of the prediction domains of the models to the spectral range covered by the analyzed peat samples indicates that many of the peat samples have MIRS different to the training data. <inline-formula><mml:math id="M240" display="inline"><mml:mrow><mml:msub><mml:mtext>HI</mml:mtext><mml:mrow><mml:mn mathvariant="normal">1630</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1090</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> as alternative decomposition indicator, C or <inline-formula><mml:math id="M241" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mi mathvariant="normal">MIRS</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, and photographs of the peat samples, suggest that samples outside prediction domains are either more decomposed or have large mineral contents (Figs. S4 and S5), which is not surprising since there are comparatively few decomposed samples and no mineral-rich samples in the training data. Data coverage by prediction domains differs between the models: 64.4 <inline-formula><mml:math id="M242" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> of the peat samples are within the prediction domain for model 1 and 2.8 <inline-formula><mml:math id="M243" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> and 0 <inline-formula><mml:math id="M244" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> for the other two models, which indicates that derivative spectra differ more between the peat and the training data data than underived spectra. Thus, the models extrapolate for more decomposed and mineral-rich peat and the prediction domain of model 1 covers most of the peat samples.</p>
</sec>
<sec id="Ch1.S3.SS3">
  <label>3.3</label><title>Relations of model residuals to N contents</title>
      <p id="d2e4330">A plot of residuals vs. N for different levels of  <inline-formula><mml:math id="M245" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> suggests that model 1 underestimates <inline-formula><mml:math id="M246" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for samples in the training data with a <inline-formula><mml:math id="M247" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> between ca. 20 <inline-formula><mml:math id="M248" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> and 40 <inline-formula><mml:math id="M249" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> and N content smaller than ca. 0.02 <inline-formula><mml:math id="M250" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="F3"/>). For the models computed with derivative spectra, this bias is smaller (Fig. <xref ref-type="fig" rid="F3"/>). This may indicate that model 1 makes less accurate predictions for the peat samples analyzed here (99 <inline-formula><mml:math id="M251" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> have a N content smaller than 0.02 <inline-formula><mml:math id="M252" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) and in general <xref ref-type="bibr" rid="bib1.bibx36" id="paren.65"/>.</p>

      <fig id="F3" specific-use="star"><label>Figure 3</label><caption><p id="d2e4422">Model residuals (measured <inline-formula><mml:math id="M253" display="inline"><mml:mrow><mml:mi mathvariant="italic">γ</mml:mi><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) vs. N or <inline-formula><mml:math id="M254" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">MIRS</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> for different levels of <inline-formula><mml:math id="M255" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> (columns) and the three models (rows). Points are averages and lines and shaded areas averages and 95 <inline-formula><mml:math id="M256" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> confidence intervals of regression models fitted to the average residuals. “Reliability” refers to how reliable the N or <inline-formula><mml:math id="M257" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">MIRS</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values are. Values of <inline-formula><mml:math id="M258" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mi mathvariant="normal">MIRS</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are less reliable when they are not in the prediction domain, which is the case only for some of the undecomposed litter samples.</p></caption>
          <graphic xlink:href="https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026-f03.png"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS4">
  <label>3.4</label><title>Predictions with additions of a silicate-rich sample</title>
      <p id="d2e4503">For silicates, prediction errors of all models increase the more silicates are mixed into the samples such that 95 <inline-formula><mml:math id="M259" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> prediction intervals cover nearly the whole range of possible values for <inline-formula><mml:math id="M260" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (Figs. S7–S9). The behavior of predicted medians differs between the models. For model 1, predictions overall increase for undecomposed samples and decrease for more decomposed samples, but the differences are never larger than ca. 30 <inline-formula><mml:math id="M261" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>. Model 3 behaves similar, but predictions always increase with more silicate influence and differences to the true value may exceed 50 <inline-formula><mml:math id="M262" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>. For model 2, predictions decrease with more silicate influence for all but the undecomposed samples and compared to the other models more posterior probability is placed on smaller degrees of decomposition.</p>
</sec>
<sec id="Ch1.S3.SS5">
  <label>3.5</label><title>Predictions with additions of strongly decomposed samples</title>
      <p id="d2e4550">For decomposed peat, the median predicted <inline-formula><mml:math id="M263" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> increases for all samples and models, as expected when adding a highly decomposed peat sample to less decomposed litter samples (Figs. S10–S12). Median predictions for the maximum addition of the decomposed peat are smallest for model 1 and largest for model 3. As for the silicate experiment, also prediction errors of all models increase the more of the decomposed sample is mixed into the samples, but prediction intervals are narrower than for the silicate experiment and, especially for already decomposed litters, their width also differs between models: Model 1 estimates the largest prediction errors and prediction errors increase the more of the decomposed peat is added to a sample, even for decomposed litter. Model 2 and in particular model 3 have narrower prediction intervals for already decomposed litter, but in most of the cases predictions do not differ significantly from those of model 1. Thus, model 1 estimates a smaller median <inline-formula><mml:math id="M264" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with larger prediction errors than the models using derivative spectra, but all models make extrapolations that are qualitatively reasonable.</p>
</sec>
<sec id="Ch1.S3.SS6">
  <label>3.6</label><title>Predictions for mixtures of different litter components</title>
      <p id="d2e4584">Predictions of all models for samples consisting of two litter types with different degree of decomposition underestimate <inline-formula><mml:math id="M265" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. As shown in Fig. <xref ref-type="fig" rid="F4"/>, the bias is well described by our theoretical expectation (Eq. <xref ref-type="disp-formula" rid="Ch1.E2"/>). Thus, the magnitude of the bias is related to the difference in <inline-formula><mml:math id="M266" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of the mixed litter types and their relative mass fractions in the mixture. This relation is non-linear; when one of the two litter types is clearly dominant (mass ratio of <inline-formula><mml:math id="M267" display="inline"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1000</mml:mn></mml:mrow></mml:math></inline-formula>), the bias vanishes, such that for mass ratios in-between these extremes, the bias reaches a maximum. This maximum value is larger the larger the difference in <inline-formula><mml:math id="M268" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> between the two litter types is. The difference in <inline-formula><mml:math id="M269" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> also controls the position of the maximum. The more decomposed one of the components is compared to the other component, the more is the maximum shifted towards a smaller mass fraction of the more decomposed component.</p>

      <fig id="F4" specific-use="star"><label>Figure 4</label><caption><p id="d2e4634">Values of <inline-formula><mml:math id="M270" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> minus <inline-formula><mml:math id="M271" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> (predicted by all three models) for mixtures of two litter types (components) vs. the mass fraction of the first component. Columns indicate the second component of the mixture (indicated by <inline-formula><mml:math id="M272" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and species) and rows indicate the first component of the mixture (indicated by <inline-formula><mml:math id="M273" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>). Point colors indicate the species of the first component. Point shapes indicate the model with which <inline-formula><mml:math id="M274" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> was predicted. The black lines are calculated with Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>) (using average coefficients from model 1).</p></caption>
          <graphic xlink:href="https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026-f04.png"/>

        </fig>

      <p id="d2e4689">There is some deviation from this pattern due to prediction errors in <inline-formula><mml:math id="M275" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for individual litter samples. Discrepancies not related to model prediction errors for individual litter types only occur when undecomposed litter of one species is mixed with strongly decomposed litter of some different species, where the mass ratio of the more decomposed litter type is between one third and two thirds (upper right and lower left panels in Fig. <xref ref-type="fig" rid="F4"/>, where diverse litter types are mixed with <italic>P. australis</italic> and where <italic>S. capillifolium</italic> litter is mixed with <italic>P. australis</italic> litter). If only undecomposed litter from different species and organs is mixed, <inline-formula><mml:math id="M276" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> correctly estimates a small <inline-formula><mml:math id="M277" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> (values range between 0–0.02 <inline-formula><mml:math id="M278" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> across all mixtures and models), which is also in line with our expectation. Overall the bias is similar across all models and for mixtures of different species and organs, and can be well described by Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>), with smaller deviations caused by prediction errors for <inline-formula><mml:math id="M279" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and variation between litter types. The bias estimated with model 2 matches the expected relation best.</p>
</sec>
<sec id="Ch1.S3.SS7">
  <label>3.7</label><title>Degree of decomposition and reconstructed NPP for peat cores</title>
      <p id="d2e4771">Figure <xref ref-type="fig" rid="F5"/> shows <inline-formula><mml:math id="M280" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and NPP of individual litter types estimated with <inline-formula><mml:math id="M281" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and the average <inline-formula><mml:math id="M282" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and total aboveground NPP for the three peat cores vs. time. For MH1, <inline-formula><mml:math id="M283" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> was smaller than 50 <inline-formula><mml:math id="M284" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> throughout the last 500 <inline-formula><mml:math id="M285" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">years</mml:mi></mml:mrow></mml:math></inline-formula>; larger values  were only estimated for two short phases around 1700 and in the last decades, where <italic>S. cuspidatum</italic> and <italic>E. vaginatum</italic> dominated and TA-WTD indicate drier conditions. The reconstructed median NPP at MH1 is larger than at the two other sites, the median was stable during the last 500 <inline-formula><mml:math id="M286" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">years</mml:mi></mml:mrow></mml:math></inline-formula> and larger than 0.1 <inline-formula><mml:math id="M287" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">kg</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>. Recent and past drying events coincide with a decrease in NPP. For MK1, the core with the oldest layers, the median <inline-formula><mml:math id="M288" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is ca. 75 <inline-formula><mml:math id="M289" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> for the fen phase and peat formed during 500–1800 CE, but similarly small as for MH1 for the intermediate layers dominated by hummock <italic>Sphagnum</italic> species (model 3 predicts a larger <inline-formula><mml:math id="M290" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> here than the other two models). The NPP was similarly large as in MH1 only in the fen phase and much smaller (median smaller than 0.15 <inline-formula><mml:math id="M291" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">kg</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) afterwards. No fen phase is covered by OD2 and <inline-formula><mml:math id="M292" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> was small and more stable than in the other cores, with only a small peak roughly during the period of the Little Ice Age. The NPP was similar to MK1. In contrast to all other cores the NPP strongly increased during the last decades in OD2. In many cases, the apparent mass accumulation rate (AMAR) is nearly identical to the reconstructed NPP, but AMAR underestimates the median NPP and decomposition mass losses for more decomposed layers. Many decomposition peaks appear to be related to peaks in reconstructed WTD (drying events) (for example MH1: ca. 1700 CE and in recent decades, MK1: ca. 1700, 1500, 1000 BCE, OD2: ca. 2700, 1700, 700, 400 BCE), but there are also WTD peaks that do not coincide with an increase in <inline-formula><mml:math id="M293" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> (also not when possible time lags between WTD and <inline-formula><mml:math id="M294" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> are considered, for example: MK1: ca. 3000 BCE, OD2: ca. 700 CE).</p>

      <fig id="F5" specific-use="star"><label>Figure 5</label><caption><p id="d2e4941">Reconstructions of <inline-formula><mml:math id="M295" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and the NPP from <inline-formula><mml:math id="M296" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for the three peat cores analyzed here. Columns show results for peat cores and rows for the three prediction models for <inline-formula><mml:math id="M297" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>. The <inline-formula><mml:math id="M298" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axis is the age of the upper boundary of the layers, measured since the coring date. Panel <bold>(a)</bold> shows <inline-formula><mml:math id="M299" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimated for taxa with a volume fraction of at least 40 <inline-formula><mml:math id="M300" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> in at least 15 samples (colored points are medians and error bars 90 <inline-formula><mml:math id="M301" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> confidence intervals) and the median <inline-formula><mml:math id="M302" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of each layer (grey shaded areas and grey line; the grey shaded areas are 50 <inline-formula><mml:math id="M303" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> and 90 <inline-formula><mml:math id="M304" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> confidence intervals). Panel <bold>(b)</bold> shows the NPP (or, in presence of roots, the initial mass accumulation rate) for taxa with a volume fraction of at least 40 <inline-formula><mml:math id="M305" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> in at least 15 samples (colored points are medians and error bars 90 <inline-formula><mml:math id="M306" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> confidence intervals), the median NPP of each layer (grey shaded areas and grey line), and the median apparent mass accumulation rate (AMAR) (brown line). The <inline-formula><mml:math id="M307" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axis is clipped at 1 <inline-formula><mml:math id="M308" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">kg</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>. Blue lines are average reconstructed WTD (normalized) More positive values indicate drier conditions. The color of the small rugs along the <inline-formula><mml:math id="M309" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axis (“Is in prediction domain?”) indicate whether the MIRS for the peat samples are within the prediction domain of the models for <inline-formula><mml:math id="M310" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>.</p></caption>
          <graphic xlink:href="https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026-f05.png"/>

        </fig>

      <p id="d2e5108">Common patterns between all models and cores are that dominance of <italic>Eriophorum</italic> sp. in peat often coincides with a large <inline-formula><mml:math id="M311" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, that a small <inline-formula><mml:math id="M312" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is estimated for the topmost layers (as expected), and that a rather small <inline-formula><mml:math id="M313" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> (<inline-formula><mml:math id="M314" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M315" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>) is estimated for many <italic>S. fuscum</italic>, <italic>S.rubellum</italic>, and <italic>S. magellanicum</italic> layers even though they are several thousands of years old (and similarly, the overall <inline-formula><mml:math id="M316" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for these layers). The dominance in <italic>Eriophorum</italic> is often preceded by an increase in <inline-formula><mml:math id="M317" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of <italic>Sphagnum</italic> peat (e.g. MK1: ca. 1300 BCE, OD2: ca. 700 and 0 BCE) and <inline-formula><mml:math id="M318" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> often only decreases after <italic>Eriophorum</italic> volume fractions are smaller again. This pattern is compatible with secondary decomposition and colonization by <italic>Eriophorum</italic> caused by drier conditions.</p>
      <p id="d2e5198">While the models indicate overall similar trends in <inline-formula><mml:math id="M319" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and NPP, values of <inline-formula><mml:math id="M320" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and NPP vary comparatively much between the three models: model 1 estimates the smallest <inline-formula><mml:math id="M321" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and NPP, model 3 the largest values, and model 2 estimates intermediate values. Model 3 does, for example, not estimate a decrease in <inline-formula><mml:math id="M322" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for MK1 during ca. 5000–4500 BCE. However, the estimated maximum values of <inline-formula><mml:math id="M323" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> per core are similar. Overall, model 3 suggests a smaller average difference in <inline-formula><mml:math id="M324" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> between phases with more decomposition losses and phases with less decomposition losses than the other two models. Large errors in <inline-formula><mml:math id="M325" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> are mainly due to extrapolation for more decomposed samples. Large errors in NPP are mainly due to dating errors (unlike many studies, we considered these errors here).</p>
      <p id="d2e5251">Our estimates for <italic>S. fuscum</italic> NPP cover the range of NPP from different studies compiled by <xref ref-type="bibr" rid="bib1.bibx15" id="text.66"/> (<inline-formula><mml:math id="M326" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.12</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.09</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M327" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">kg</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, average <inline-formula><mml:math id="M328" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> standard deviation) <xref ref-type="bibr" rid="bib1.bibx40 bib1.bibx52 bib1.bibx56 bib1.bibx62 bib1.bibx77" id="paren.67"/>, and are contained in the wider NPP range measured in monospecific <italic>S. fuscum</italic> patches in <xref ref-type="bibr" rid="bib1.bibx11" id="text.68"/> (<inline-formula><mml:math id="M329" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.21</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.14</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M330" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">kg</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx10" id="paren.69"/> or other studies <xref ref-type="bibr" rid="bib1.bibx86 bib1.bibx87" id="paren.70"/>. While it is not surprising that our estimates are within these broad ranges, it is reassuring to see that median estimates produced with the suggested approach do not obviously contradict expected ranges for NPP.</p>
</sec>
<sec id="Ch1.S3.SS8">
  <label>3.8</label><title>Relation between saturated hydraulic conductivity and <inline-formula><mml:math id="M331" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula></title>
      <p id="d2e5369">The estimated relation between MIRS-estimated saturated hydraulic conductivity (<inline-formula><mml:math id="M332" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) and <inline-formula><mml:math id="M333" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for the three peat cores and with <inline-formula><mml:math id="M334" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimated from <inline-formula><mml:math id="M335" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> predicted by the three models is shown in Fig. <xref ref-type="fig" rid="F6"/>, together with <inline-formula><mml:math id="M336" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M337" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> relations suggested in earlier studies. At least for the cores analyzed here, default parameterizations differ from estimated averages (albeit one has to consider that both <inline-formula><mml:math id="M338" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M339" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimates have relatively large errors): In contrast to the relation implemented in the Holocene Peatland Model (Eq. <xref ref-type="disp-formula" rid="Ch1.E4"/>), the data suggest that <inline-formula><mml:math id="M340" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> decreases continuously with <inline-formula><mml:math id="M341" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and our data do not cover ranges of <inline-formula><mml:math id="M342" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> large enough to test the suggested step-like decrease for strongly decomposed peat. The relation suggested in <xref ref-type="bibr" rid="bib1.bibx42" id="text.71"/> and used in the DigiBog model overestimates <inline-formula><mml:math id="M343" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and estimates a too strong decrease of <inline-formula><mml:math id="M344" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with <inline-formula><mml:math id="M345" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. The relation suggested in <xref ref-type="bibr" rid="bib1.bibx44" id="text.72"/> fits our estimates well, but the estimated depth dependence is too strong. For example, if a depth of 50 <inline-formula><mml:math id="M346" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">cm</mml:mi></mml:mrow></mml:math></inline-formula> is assumed for all samples, <inline-formula><mml:math id="M347" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> would be underestimated, as shown in Fig. <xref ref-type="fig" rid="F6"/>; in contrast our estimates suggest a less strong control of depth (<inline-formula><mml:math id="M348" display="inline"><mml:mo lspace="0mm">≈</mml:mo></mml:math></inline-formula> total stress) on <inline-formula><mml:math id="M349" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for our cores.</p>

      <fig id="F6" specific-use="star"><label>Figure 6</label><caption><p id="d2e5552">Relation between MIRS-predicted saturated hydraulic conductivity (<inline-formula><mml:math id="M350" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) and <inline-formula><mml:math id="M351" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for the three peat cores analyzed here (columns) and with <inline-formula><mml:math id="M352" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> predicted by one of the three models (rows). Points are average estimates and error bars are 90 <inline-formula><mml:math id="M353" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> prediction intervals. Point colors indicate the depth of the peat layers. Point shapes indicate whether MIRS from which <inline-formula><mml:math id="M354" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> was predicted are within the training prediction domain of the model (“yes”) or not (“no”). Predictions outside the prediction domain may have larger errors than estimated. The lines are <inline-formula><mml:math id="M355" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M356" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> relations suggested in the literature (see the text for details).</p></caption>
          <graphic xlink:href="https://bg.copernicus.org/articles/23/5549/2026/bg-23-5549-2026-f06.png"/>

        </fig>

</sec>
</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Discussion</title>
      <p id="d2e5638">To address the problem of estimating <inline-formula><mml:math id="M357" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for peat samples, we developed and evaluated a novel decomposition indicator, <inline-formula><mml:math id="M358" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, and developed the mathematical tools necessary to estimate <inline-formula><mml:math id="M359" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> with <inline-formula><mml:math id="M360" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> even for complex mixtures of several litter types with different <inline-formula><mml:math id="M361" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. This enabled us to analyze in detail <inline-formula><mml:math id="M362" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and the past NPP for three peat cores based on bulk MIRS. Overall, this suggests that the approach developed here is a promising first step towards accurate estimation of peat <inline-formula><mml:math id="M363" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and reconstruction of past NPP. As is the case for all novel and complex prediction models, intensive testing is required to address remaining limitations and reduce prediction errors and some of this work remains to be done by future studies. The diverse palette of tests used here both shows that <inline-formula><mml:math id="M364" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> can be estimated with <inline-formula><mml:math id="M365" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with reasonably small errors for the various litter types considered here, and helps to identify limitations and possible future improvements.</p>
      <p id="d2e5717">In the next subsections, we synthesize the mixing model approach to compensate the bias in <inline-formula><mml:math id="M366" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for mixtures of litter types (Sect. <xref ref-type="sec" rid="Ch1.S4.SS1"/>), we synthesize the evaluation of the prediction models, and we identify limitations which can be addressed in future studies (Sect. <xref ref-type="sec" rid="Ch1.S4.SS2"/>). We also discuss how the approach developed here can be even further improved to estimate <inline-formula><mml:math id="M367" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and reconstruct the NPP, how <inline-formula><mml:math id="M368" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> can be linked to process models and what other research questions may be addressed and illustrate this with our analysis of the three peat cores (Sect. <xref ref-type="sec" rid="Ch1.S4.SS3"/>).</p>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><title>Estimating <inline-formula><mml:math id="M369" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> from <inline-formula><mml:math id="M370" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for mixtures of litter types</title>
      <p id="d2e5782">As outlined in the Introduction, <inline-formula><mml:math id="M371" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is biased when litter types with different <inline-formula><mml:math id="M372" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> are mixed. Our results suggests that Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>) reasonably well fits <inline-formula><mml:math id="M373" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for mixtures of litter types; larger deviations only occur for litter mixtures that are probably rare under natural conditions (mixtures of one to two thirds of an undecomposed litter with a two to one thirds of a strongly decomposed litter). Moreover, at least for models 2, these deviations are small compared to prediction errors. Thus, since Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>) reasonably well fits <inline-formula><mml:math id="M374" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for mixtures of litter types and since <inline-formula><mml:math id="M375" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> fits <inline-formula><mml:math id="M376" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of individual litter types well, the bias can be avoided or corrected.</p>
      <p id="d2e5848">There are three possible approaches to avoid or correct this bias: The first approach is to use bulk <inline-formula><mml:math id="M377" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> measurements and information on the relative mass fractions of each litter type in the sample (for example from macrofossil analysis) to estimate <inline-formula><mml:math id="M378" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> from <inline-formula><mml:math id="M379" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with the mixing model (Eq. <xref ref-type="disp-formula" rid="Ch1.E3"/>) developed here (workflow (1) in Fig. <xref ref-type="fig" rid="F1"/>); this corrects the bias. The second approach is to measure MIRS for the separate litter types and weigh the litter types (component-specific analysis; workflow (2) in Fig. <xref ref-type="fig" rid="F1"/>). In these cases, <inline-formula><mml:math id="M380" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> can be estimated for each litter type and, with reasonable prediction errors, equals <inline-formula><mml:math id="M381" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. This can be used to estimate the initial mass of the litter types, <inline-formula><mml:math id="M382" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, from <inline-formula><mml:math id="M383" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with: <inline-formula><mml:math id="M384" display="inline"><mml:mrow><mml:msub><mml:mi>m</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>m</mml:mi><mml:mo>(</mml:mo><mml:msub><mml:mi>t</mml:mi><mml:mn mathvariant="normal">0</mml:mn></mml:msub><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. Then, Eq. (<xref ref-type="disp-formula" rid="Ch1.E2"/>) can be used to compute <inline-formula><mml:math id="M385" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of the entire sample; this approach avoids the bias. The third option is a combination of the first and second approach, where a component-specific analysis is conducted only for some litter types.</p>
      <p id="d2e5995">The second approach can be used to estimate <inline-formula><mml:math id="M386" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> more accurately, both for the sample and individual litter types, than is possible with the first approach This is particularly relevant for litter types that have only a small mass fraction because the mixing model cannot estimate <inline-formula><mml:math id="M387" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> very accurately for these litter types (for this reason, we only evaluated mixing model results for litter types with a macrofossil abundance of at least 40 <inline-formula><mml:math id="M388" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> in the peat samples). Even though the sample <inline-formula><mml:math id="M389" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is less sensitive to the values of litter types with small mass fraction than <inline-formula><mml:math id="M390" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of these litter types, also estimates for the sample <inline-formula><mml:math id="M391" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> will have smaller errors. The third option shares this advantage and may be an option when it is difficult to separate all litter types (for example when litter types are strongly decomposed).</p>
      <p id="d2e6043">This points to a possible practical difficulty: it is not yet clear how to exactly define litter types and mass fractions such as to avoid biases. The mixing model and the component-specific analysis require litter types to be separated, but future studies will need to test which plant organs need to be separated to avoid biases. For example, it is quite clear that tree branches will decompose at a different rate than leaves and therefore both need to be treated as separate litter types to avoid biases. But does the same apply, for example, also to <italic>Sphagnum</italic> branches vs. stems? Here, we assumed that macrofossil volume fractions are directly proportional to mass fractions, as is done in process models, but this assumption is not well tested. Peat layers may also consist of peat formed over a long time range that is strongly compressed and may therefore consist of not much decomposed parts and strongly decomposed parts. In such cases, it may not be sufficient to define litter types only via taxonomic information because litter from the same species may have a large range of <inline-formula><mml:math id="M392" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> values in such layers. On the other hand, component-specific analysis can be used to determine whether <inline-formula><mml:math id="M393" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of two litter types is sufficiently similar throughout the decomposition process such that the bias in <inline-formula><mml:math id="M394" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is only small and both may therefore be treated as same litter type.</p>
      <p id="d2e6074">Overall, it is exciting to see that the possibility to estimate <inline-formula><mml:math id="M395" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> raises these issues and offers opportunities to test them and therefore to better understand peat chemistry and degree of decomposition.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><title>Which properties of an ideal decomposition indicator does <inline-formula><mml:math id="M396" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> fulfill and where are there still limitations?</title>
      <p id="d2e6104">The main question we want to address here is to what extent the prediction models for <inline-formula><mml:math id="M397" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> fulfill the properties of an ideal decomposition indicator suggested in the Introduction and compared to previous studies: <list list-type="order"><list-item>
      <p id="d2e6120"><italic>Linear relation to </italic><inline-formula><mml:math id="M398" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula><italic>.</italic> Our model evaluation suggests that all three models fit <inline-formula><mml:math id="M399" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of individual litter types with reasonable errors and no overall bias (Fig. <xref ref-type="fig" rid="F2"/>). For litter similar to the training data, prediction errors are comparable to or slightly larger than errors between litterbag replicates <xref ref-type="bibr" rid="bib1.bibx72" id="paren.73"><named-content content-type="pre">e.g.</named-content></xref> and therefore currently acceptable for many applications. Predictions for novel litter types should be treated with caution since there might be biases (Fig. <xref ref-type="fig" rid="F2"/>), however the dataset here already covers quite many different litter types and therefore we expect that this risk is small, except for woody plant organs which are currently underrepresented in the training data. Overall, <inline-formula><mml:math id="M400" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is linearly related to <inline-formula><mml:math id="M401" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of individual litter types.</p>
      <p id="d2e6168">The carbon to nitrogen ratio (C<inline-formula><mml:math id="M402" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>N) and a humification index (<inline-formula><mml:math id="M403" display="inline"><mml:mrow><mml:msub><mml:mtext>HI</mml:mtext><mml:mrow><mml:mn mathvariant="normal">1630</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1090</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula>) often used as decomposition indicators <xref ref-type="bibr" rid="bib1.bibx17 bib1.bibx12" id="paren.74"><named-content content-type="pre">e.g.</named-content></xref> have more variable relations to the measured <inline-formula><mml:math id="M404" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for the same litter types (compare supporting Figs. S13  to <xref ref-type="fig" rid="F2"/>).</p></list-item><list-item>
      <p id="d2e6209"><italic>Tested against litterbag data.</italic> While there are gaps in our training data, we are not aware of other studies that test prediction of <inline-formula><mml:math id="M405" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> with decomposition indicators with an as diverse set of litter samples as done here.</p></list-item><list-item>
      <p id="d2e6222"><italic>No confounding by differences in litter chemistry.</italic> The models successfully fit <inline-formula><mml:math id="M406" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for many diverse litter types. Whilst decomposed litter samples are underrepresented in the training data, undecomposed samples from many different taxa and all relevant plant functional types (non-<italic>Sphagnum</italic> mosses, <italic>Sphagnum</italic> mosses, sedges, herbs, shrubs, and trees) have a good fit in the model and, in most cases, also in the stratified CV. Also mixtures of different litter types are well predicted when the bias in <inline-formula><mml:math id="M407" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is compensated. Overall, this indicates that our models only have a small bias for different litter types.</p></list-item><list-item>
      <p id="d2e6252"><italic>No confounding by minerals.</italic> MIRS are strongly impacted by silicates. It will therefore be unlikely, at least with the simple linear prediction models developed here, to accurately predict <inline-formula><mml:math id="M408" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> from MIRS. For this reason, it is encouraging that <inline-formula><mml:math id="M409" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> has large prediction errors when mineral contents increase; conversely to <inline-formula><mml:math id="M410" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, humification indices indicate a smaller <inline-formula><mml:math id="M411" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for samples with mineral admixtures and therefore are biased by silicates <xref ref-type="bibr" rid="bib1.bibx17" id="paren.75"><named-content content-type="pre">e.g.</named-content></xref>.</p></list-item><list-item>
      <p id="d2e6299"><italic>No confounding when mixing litter types.</italic> While <inline-formula><mml:math id="M412" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is a biased estimator for <inline-formula><mml:math id="M413" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for litter mixtures, this bias can be corrected, as discussed in the previous subsection. We also emphasize that such a bias is not specific to <inline-formula><mml:math id="M414" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, but is a property of any decomposition indicator that measures a property where weights when computing averages for samples depend on <inline-formula><mml:math id="M415" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, which is the case for nearly all decomposition indicators (all we are aware of except for <inline-formula><mml:math id="M416" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>ARM</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>).</p></list-item></list></p>
      <p id="d2e6351">Predicting <inline-formula><mml:math id="M417" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is a complex task and as any complex method, <inline-formula><mml:math id="M418" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> has limitations, many of which can be addressed in future studies: <list list-type="order"><list-item>
      <p id="d2e6374"><italic>Variability between models.</italic> Currently, it is difficult to recommend a best model because the models have trade-offs that need to be evaluated with additional data. Our recommendation is to consider the variability of model predictions while taking into account known biases (see the next point) until further tests have been performed. While confidence intervals of <inline-formula><mml:math id="M419" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimated by the models overlap even for samples outside of the prediction domain, the large variability indicates that at least some of these predictions are biased. Overall, we assume that predictions of model 2 are most accurate because model 1 underestimates <inline-formula><mml:math id="M420" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for litter with small N content and model 3 probably overestimates <inline-formula><mml:math id="M421" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for more decomposed samples.</p></list-item><list-item>
      <p id="d2e6401"><italic>Limitations of individual models.</italic> Model 1 fits the data worst and underestimates <inline-formula><mml:math id="M422" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> most for <italic>T. latifolia</italic> and <italic>S. capillifolium</italic> samples with N content <inline-formula><mml:math id="M423" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.02</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M424" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> and therefore probably underestimates <inline-formula><mml:math id="M425" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for many peat samples and compared to the other two models. However, it has the best average predictive performance in the stratified CV, which we think best approximates possible applications of the models to peat samples, and it is also the model that confounds the least differences in initial litter chemistry with decomposition in the CV (Fig. <xref ref-type="fig" rid="F2"/>).</p>
      <p id="d2e6456">Model 3 overfits the data most, based on the stratified CV, and confounds the most differences in initial litter chemistry with decomposition in the CV (Fig. <xref ref-type="fig" rid="F2"/>), but when trained on all data, it fits <inline-formula><mml:math id="M426" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> best and does not confound difference in the chemistry of decomposed litter with decomposition, and it does not underestimate <inline-formula><mml:math id="M427" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for <italic>T. latifolia</italic> and <italic>S. capillifolium</italic> samples with N content <inline-formula><mml:math id="M428" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.02</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M429" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">g</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>. For more decomposed samples, model 3 may overestimate <inline-formula><mml:math id="M430" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, as indicated by high <inline-formula><mml:math id="M431" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimates in the analysis of the peat cores (Fig. <xref ref-type="fig" rid="F5"/>) and underestimation of the theoretically expected bias for mixtures of undecomposed and very decomposed components (Fig. <xref ref-type="fig" rid="F4"/>).</p>
      <p id="d2e6527">In all aspects mentioned in the previous two points, model 2 is intermediate between the other two models and in addition has the best average predictive performance in the stratified CV (Fig. <xref ref-type="fig" rid="F2"/>) and best compensates the bias for mixtures of litters (Fig. <xref ref-type="fig" rid="F4"/>). However, even though 95 <inline-formula><mml:math id="M432" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> prediction intervals also cover the complete possible range for samples with large mineral contents, the median predicted degree of decomposition and bulk of the posterior distribution decrease the more silicates are within a sample, which means that <inline-formula><mml:math id="M433" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> is underestimated for samples with large silicate contents.</p></list-item><list-item>
      <p id="d2e6550"><italic>Prediction domain coverage.</italic> It would be useful to include material from more litter types (in particular woody plant organs but also other samples from species measured here) and samples with larger <inline-formula><mml:math id="M434" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> than is currently the case in order to reduce extrapolation errors of the models for new litter types and more decomposed peat samples.</p></list-item><list-item>
      <p id="d2e6563"><italic>Confounding by carbonates.</italic> We could not test whether <inline-formula><mml:math id="M435" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is biased by admixtures of carbonates which can be relevant in fen peat. It is likely that carbonate-rich samples confound <inline-formula><mml:math id="M436" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> because peaks caused by carbonates interfere with peaks caused by aromatics and proteins <xref ref-type="bibr" rid="bib1.bibx63" id="paren.76"/>.</p></list-item><list-item>
      <p id="d2e6594"><italic>Modeling approach.</italic> We used a modeling approach that is robust against overfitting with relatively small sample sizes, but there are more flexible modeling approaches <xref ref-type="bibr" rid="bib1.bibx82" id="paren.77"><named-content content-type="pre">e.g.</named-content></xref> that may have smaller prediction errors or may better fit more diverse litter types or even make more accurate predictions for samples with minerals or carbonates. These modeling approaches need larger and more homogeneous datasets to avoid overfitting.</p></list-item><list-item>
      <p id="d2e6605"><italic>Limitations of the mixing model.</italic> We developed a simple mixing model that corrects the bias in <inline-formula><mml:math id="M437" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and also estimates <inline-formula><mml:math id="M438" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of individual litter types. Beside the open questions mentioned in the previous subsection, we suggest that this model can be extended to incorporate additional information. For example, we did not incorporate prior information on differences in decomposition rates between litter types which may lead to more accurate estimates for <inline-formula><mml:math id="M439" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>. A natural extension of the mixing model is to link it to a process model that constrains <inline-formula><mml:math id="M440" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of individual litter types.</p></list-item></list></p>
      <p id="d2e6642">While not considered here, an additional limitation of the current litterbag data may be that they do not consider how litter preprocessing may bias mass losses from decomposition compared to decomposition under more natural conditions <xref ref-type="bibr" rid="bib1.bibx5 bib1.bibx72" id="paren.78"><named-content content-type="pre">e.g.</named-content></xref>. This may confound relations between MIRS and <inline-formula><mml:math id="M441" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> under more natural conditions when making predictions with models trained on litterbag data. However, the extent of this problem remains unclear at present.</p>
      <p id="d2e6658">Overall, this evaluation suggests that <inline-formula><mml:math id="M442" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> fulfills many properties of an ideal decomposition indicator, even if not applicable to all peat samples. Despite many opportunities for improvements, we are not aware of a decomposition indicator that has the potential to predict <inline-formula><mml:math id="M443" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> as well as does <inline-formula><mml:math id="M444" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and that can be as easily measured, even with small sample amounts, as is the case for <inline-formula><mml:math id="M445" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>.</p>
</sec>
<sec id="Ch1.S4.SS3">
  <label>4.3</label><title>Implications for peatland research and peatland restoration</title>
      <p id="d2e6710">Here, we discuss some problems in peatland research and restoration that may be addressed with <inline-formula><mml:math id="M446" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and illustrate some of these points with our analysis of the three mountain bog cores. <list list-type="order"><list-item>
      <p id="d2e6726"><italic>Estimation of long-term decomposition rates and improvement of process models.</italic> Our analysis of the peat cores suggests a quite large variation in <inline-formula><mml:math id="M447" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> for hummock <italic>Sphagnum</italic> species, with several peaks across the entire depth, even if the peat is several thousands of years old. These differences were probably caused by differences in aerobic decomposition losses since catotelm decomposition rates are assumed to vary less with depth and over time and since at least some layers with larger hummock <italic>Sphagnum</italic> <inline-formula><mml:math id="M448" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> coincide with or precede WTD peaks (Fig. <xref ref-type="fig" rid="F5"/>) <xref ref-type="bibr" rid="bib1.bibx45" id="paren.79"/>. Preservation of such variations in peat may allow to better estimate long-term decomposition rates of plant functional types and reconstruct past environmental conditions with process models.</p>
      <p id="d2e6757">It is interesting that a small <inline-formula><mml:math id="M449" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> (smaller than 50 <inline-formula><mml:math id="M450" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>, median values smaller than 25 <inline-formula><mml:math id="M451" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula>) is suggested by all three models (even model 3 that may overestimate <inline-formula><mml:math id="M452" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, Fig. <xref ref-type="fig" rid="F5"/>) for hummock <italic>Sphagnum</italic> litter in some of the peat samples several hundreds or even thousands of years old and from all three peat cores. Some studies suggest much larger figures for <inline-formula><mml:math id="M453" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx20 bib1.bibx58" id="paren.80"/>, whereas other studies suggest values for <inline-formula><mml:math id="M454" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> similar to those found here <xref ref-type="bibr" rid="bib1.bibx89 bib1.bibx51" id="paren.81"/>. A litterbag synthesis suggests that under aerobic conditions, <italic>S. fuscum</italic> may lose 50 <inline-formula><mml:math id="M455" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> of its initial mass after 20–50 <inline-formula><mml:math id="M456" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">years</mml:mi></mml:mrow></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx73" id="paren.82"/>. Assuming a catotelm decomposition rate of 0.0004 <inline-formula><mml:math id="M457" display="inline"><mml:mrow class="unit"><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, this would lead to an additional mass loss of ca. 15 <inline-formula><mml:math id="M458" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> over 1000 <inline-formula><mml:math id="M459" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">years</mml:mi></mml:mrow></mml:math></inline-formula> and thus a mass loss ca. 20 <inline-formula><mml:math id="M460" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> larger than the upper 90 <inline-formula><mml:math id="M461" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> confidence interval of <inline-formula><mml:math id="M462" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> predicted for these samples. This may suggest either that litterbag experiments overestimate decomposition rates (at least under these conditions), that the time until incorporation into the catotelm was even shorter than 20–50 <inline-formula><mml:math id="M463" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">years</mml:mi></mml:mrow></mml:math></inline-formula>, or that other factors than moisture limited decomposition during these periods (e.g. thermodynamic constraints in the catotelm <xref ref-type="bibr" rid="bib1.bibx7 bib1.bibx14" id="altparen.83"><named-content content-type="pre">e.g.</named-content></xref>, colder temperatures, etc.). When linked to process models, <inline-formula><mml:math id="M464" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> may help to address these questions and therefore to better understand long-term decomposition losses.</p>
      <p id="d2e6917">Other open problems that may be addressed with <inline-formula><mml:math id="M465" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> are: (1) A more precise quantification of differences in decomposition rates between litter types. If (aboveground) litter from the same layer decomposed under the same environmental conditions, current decomposition models <xref ref-type="bibr" rid="bib1.bibx28" id="paren.84"><named-content content-type="pre">e.g.</named-content></xref> assume that differences in <inline-formula><mml:math id="M466" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> rates are only controlled by differences in the maximum possible decomposition rates of these litter types. This allows to estimate differences or ratios of litter type-specific decomposition rates from <inline-formula><mml:math id="M467" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> of individual litter types (supporting information Sect. S5). (2) It is commonly assumed that decomposition rates slow down the more of the initial mass has already been decomposed and this is an important control of long-term peat accumulation rates <xref ref-type="bibr" rid="bib1.bibx28 bib1.bibx21" id="paren.85"><named-content content-type="pre">e.g.</named-content></xref>. However, this slow-down is difficult to quantify <xref ref-type="bibr" rid="bib1.bibx28 bib1.bibx21" id="paren.86"/> because the effect only manifests over long time periods not covered by litterbag experiments and because of difficulties to accurately estimate decomposition parameters from peat cores; measurements of <inline-formula><mml:math id="M468" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> from many peat cores and samples across large time gradients may help to address this problem (supporting information Sect. S5). (3) Similarly to the slow-down due to decreasing litter quality, it is assumed that anaerobic decomposition rates decrease with depth due to thermodynamic limitations <xref ref-type="bibr" rid="bib1.bibx7 bib1.bibx14" id="paren.87"><named-content content-type="pre">e.g.</named-content></xref>, which can have large effects on long-term peat accumulation <xref ref-type="bibr" rid="bib1.bibx49" id="paren.88"/>. Measurements of <inline-formula><mml:math id="M469" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> may complement targeted litterbag experiments to better estimate this decrease in anaerobic decomposition rates <xref ref-type="bibr" rid="bib1.bibx73 bib1.bibx29" id="paren.89"/>.</p></list-item><list-item>
      <p id="d2e6997"><italic>Analysis of the WTD-decomposition feedback.</italic> Saturated hydraulic conductivity (<inline-formula><mml:math id="M470" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) is an important control of peatland WTD and depends on the pore size distribution which in turn depends on the stiffness of the organic matter <xref ref-type="bibr" rid="bib1.bibx37" id="paren.90"><named-content content-type="pre">e.g.</named-content></xref>. Decomposition decreases the stiffness and therefore facilitates pore collapse, implying that <inline-formula><mml:math id="M471" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M472" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> are negatively related <xref ref-type="bibr" rid="bib1.bibx42" id="paren.91"><named-content content-type="pre">e.g.</named-content></xref>. Several studies hypothesized relations between saturated hydraulic conductivity (<inline-formula><mml:math id="M473" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) and <inline-formula><mml:math id="M474" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> (<xref ref-type="bibr" rid="bib1.bibx29" id="altparen.92"/> with corrected formulas as included in the Supplement to <xref ref-type="bibr" rid="bib1.bibx78 bib1.bibx42 bib1.bibx44 bib1.bibx37 bib1.bibx38" id="altparen.93"/>), but these hypotheses could only be evaluated against not well tested proxies of <inline-formula><mml:math id="M475" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula>, such as ratios of C<inline-formula><mml:math id="M476" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>N values <xref ref-type="bibr" rid="bib1.bibx44" id="paren.94"/>, if at all. To illustrate how <inline-formula><mml:math id="M477" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> may contribute to testing these hypotheses, we predicted <inline-formula><mml:math id="M478" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for the peat samples analyzed here from MIRS and plotted these predictions vs. <inline-formula><mml:math id="M479" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> together with the suggested <inline-formula><mml:math id="M480" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M481" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> relations (Fig. <xref ref-type="fig" rid="F6"/>). The results indicate that, at least for the cores analyzed here, default parameterizations differ from estimated averages (albeit one has to consider that both <inline-formula><mml:math id="M482" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M483" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> estimates have relatively large errors). Estimation of <inline-formula><mml:math id="M484" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> from peat MIRS would also allow to test the relation between <inline-formula><mml:math id="M485" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and Young's modulus suggested in <xref ref-type="bibr" rid="bib1.bibx37" id="text.95"/> and <xref ref-type="bibr" rid="bib1.bibx38" id="text.96"/>, and thus also the suggested relations to porosity, bulk density, and <inline-formula><mml:math id="M486" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> suggested therein, if measurements for Young's modulus of peat would be available. Our analysis indicates that <inline-formula><mml:math id="M487" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> may be useful to estimate processes relevant to better understand the ecohydrological feedback in peatlands and to improve existing peatland models.</p></list-item><list-item>
      <p id="d2e7196"><italic>Definition of reference states for restoration and long-term monitoring of peatland states.</italic> Peatland restoration usually aims to restore the peat accumulation function by increasing NPP and reducing decomposition losses. Here, <inline-formula><mml:math id="M488" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> can be useful to define baselines for the NPP of individual species and the overall NPP, and what fraction of the initial mass should be transferred from the acrotelm to the catotelm. For example, based on our results, one may target a NPP of ca. 0.2 <inline-formula><mml:math id="M489" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">kg</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> at MH1 as historical reference state for restoration since this corresponds to the past average NPP over several centuries where the small <inline-formula><mml:math id="M490" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> indicates that much of this sequestered C is stored in the catotelm. Our analysis also suggests that a drying trend during the last decades halved the NPP (Fig. <xref ref-type="fig" rid="F5"/>). Here, <inline-formula><mml:math id="M491" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> allows to distinguish between a reduction in NPP vs. an increase in decomposition losses. While a process model analysis is necessary to estimate net mass or carbon balances <xref ref-type="bibr" rid="bib1.bibx90" id="paren.97"/>, a decrease in NPP and increase in <inline-formula><mml:math id="M492" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of surface peat very likely indicate a decrease in the net mass or carbon balance since the acrotelm contributes most to decomposition losses. Considering that no long-term measurements of gas fluxes are required to obtain this information, but only standard analyses of peat cores, this may be a cost-efficient approach to estimate how much the current state of a peatland differs from reference states in the past and to evaluate restoration over longer time periods. Our analysis also illustrates the possibility to define site-specific reference states for NPP of target communities that were realized at the site over long time periods because <inline-formula><mml:math id="M493" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> allows to infer that NPP has probably always been smaller at MK1 and OD2 than at MH1 (Fig. <xref ref-type="fig" rid="F5"/>). The rather large errors in the reconstruction here can be reduced not only by improving prediction of <inline-formula><mml:math id="M494" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, but also by more precise dating and by replacing MIRS-predicted bulk densities with bulk density measurements.</p></list-item></list></p>
      <p id="d2e7293">In summary, this suggests that <inline-formula><mml:math id="M495" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> may be useful to better understand peat accumulation, improve process models, define baselines for peatland restoration, and monitor long-term restoration trajectories.</p>
</sec>
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<sec id="Ch1.S5" sec-type="conclusions">
  <label>5</label><title>Conclusions</title>
      <p id="d2e7316">To address the question whether it is possible to estimate <inline-formula><mml:math id="M496" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of peat samples, we developed models that predict <inline-formula><mml:math id="M497" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> measured in litterbag experiments from MIRS (<inline-formula><mml:math id="M498" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) and a mixing model that compensates biases in <inline-formula><mml:math id="M499" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for mixtures of litter types and therefore allows to estimate <inline-formula><mml:math id="M500" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> from <inline-formula><mml:math id="M501" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> with bulk MIRS measurements.</p>
      <p id="d2e7374">Our model evaluation suggests that the models accurately fit <inline-formula><mml:math id="M502" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of several litter types, that the models do not confound differences in litter chemistry or additions of minerals with decomposition, and that our mixing model can correct underestimation of <inline-formula><mml:math id="M503" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> by <inline-formula><mml:math id="M504" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> for litter mixtures with known mass fraction of each component, which allows to estimate <inline-formula><mml:math id="M505" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of dominant components, to estimate the average <inline-formula><mml:math id="M506" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> of the sample, and to reconstruct the aboveground NPP (in absence of roots) of dominant litter types and the entire vegetation community at the sampling location.</p>
      <p id="d2e7417">As is the case for all novel and complex prediction models, intensive testing is required to address remaining limitations and reduce prediction errors and some of this work remains to be done by future studies. Main limitations are that there is a relatively large variability in median predictions of <inline-formula><mml:math id="M507" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> between prediction models using differently preprocessed MIRS due to biases for litter with small N contents (model 1), possible overfitting (model 2 and 3), extrapolation for more decomposed peat samples and therefore larger prediction errors (all models), large prediction errors for mineral-rich samples, missing woody plant organs in the training data, and possible limitations we could not test here (for example the influence of carbonates). Despite these limitations, <inline-formula><mml:math id="M508" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> fulfills many of the properties of an ideal decomposition indicator and is a promising first step towards accurate estimation of peat <inline-formula><mml:math id="M509" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and reconstruction of past NPP, in particular compared to the ash residue method, which has large errors, and other decomposition indicators, which cannot estimate <inline-formula><mml:math id="M510" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> quantitatively.</p>
      <p id="d2e7452">Our analysis of three mountain bog peat cores illustrates that, if the limitations of the models are considered, <inline-formula><mml:math id="M511" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> may be useful to estimate <inline-formula><mml:math id="M512" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> and reconstruct past aboveground NPP for individual litter types and peat samples. We discussed that these estimates of <inline-formula><mml:math id="M513" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> may be useful to address a number of questions relevant to understand peatland processes and to plan and monitor peatland restoration (in particular when studies measure MIRS for individual litter types): Estimating long-term rates of peat decomposition, using peat cores as long-term litterbag experiments to understand environmental controls (thermodynamics limitations, decrease of litter quality), testing hypotheses about long-term decomposition processes (e.g. the time taken to incorporate peat into the catotelm), estimating the feedback between decomposition and peat hydraulic properties (e.g. the <inline-formula><mml:math id="M514" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M515" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> relation), and definition of past reference states for NPP and decomposition losses. Preliminary results indicate that <italic>Sphagnum</italic> peat can have a small <inline-formula><mml:math id="M516" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> even if it is several hundreds to thousands years old, and that at, least for the cores analyzed here, suggested <inline-formula><mml:math id="M517" display="inline"><mml:mrow><mml:msub><mml:mi>K</mml:mi><mml:mtext>sat</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M518" display="inline"><mml:mi mathvariant="italic">γ</mml:mi></mml:math></inline-formula> relations differ from the averages estimated here and vary between peat cores.</p>
      <p id="d2e7528">Thus, <inline-formula><mml:math id="M519" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">γ</mml:mi><mml:mtext>MIRS</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> may be useful to improve understanding of peat accumulation dynamics, process models, and may be used for a cost-efficient definition of peatland reference states and monitoring restoration trajectories.</p>
</sec>

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

      <p id="d2e7547">Peat data are available from the Peatland Mid-Infrared Database (<ext-link xlink:href="https://doi.org/10.5281/zenodo.17092587" ext-link-type="DOI">10.5281/zenodo.17092587</ext-link>, <xref ref-type="bibr" rid="bib1.bibx70" id="altparen.98"/>). Litter data are available from the Peatland Mid-Infrared Database (undecomposed litter, data from <xref ref-type="bibr" rid="bib1.bibx53" id="altparen.99"/>,  <ext-link xlink:href="https://doi.org/10.1594/PANGAEA.902069" ext-link-type="DOI">10.1594/PANGAEA.902069</ext-link> and <xref ref-type="bibr" rid="bib1.bibx54" id="altparen.100"/>,  <ext-link xlink:href="https://doi.org/10.1594/PANGAEA.902176" ext-link-type="DOI">10.1594/PANGAEA.902176</ext-link>), and <xref ref-type="bibr" rid="bib1.bibx3" id="text.101"/> (<ext-link xlink:href="https://doi.org/10.5281/zenodo.10581235" ext-link-type="DOI">10.5281/zenodo.10581235</ext-link>; all data except spectra, which are available from <xref ref-type="bibr" rid="bib1.bibx71" id="altparen.102"/>, <ext-link xlink:href="https://doi.org/10.5281/zenodo.17209547" ext-link-type="DOI">10.5281/zenodo.17209547</ext-link>). The code to reproduce this manuscript and the mid-infrared spectra for samples in <xref ref-type="bibr" rid="bib1.bibx3" id="text.103"/> are available from <xref ref-type="bibr" rid="bib1.bibx75" id="text.104"/> (<ext-link xlink:href="https://doi.org/10.5281/zenodo.21574541" ext-link-type="DOI">10.5281/zenodo.21574541</ext-link>). An R-package to estimate the mixing model for peat samples is available from <xref ref-type="bibr" rid="bib1.bibx66" id="text.105"/> (<ext-link xlink:href="https://doi.org/10.5281/zenodo.17209338" ext-link-type="DOI">10.5281/zenodo.17209338</ext-link>). The models to predict γMIRS are implemented in the irpeatmodels package <xref ref-type="bibr" rid="bib1.bibx65" id="paren.106"/> (<ext-link xlink:href="https://doi.org/10.5281/zenodo.17187912" ext-link-type="DOI">10.5281/zenodo.17187912</ext-link>) that can be used with the irpeat package  (<xref ref-type="bibr" rid="bib1.bibx67" id="altparen.107"/>, <ext-link xlink:href="https://doi.org/10.5281/zenodo.17200517" ext-link-type="DOI">10.5281/zenodo.17200517</ext-link>).</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d2e7610">The supplement related to this article is available online at <inline-supplementary-material xlink:href="https://doi.org/10.5194/bg-23-5549-2026-supplement" xlink:title="pdf">https://doi.org/10.5194/bg-23-5549-2026-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d2e7619">HT: Conceptualization, methodology, software, validation, formal analysis, investigation, visualization, writing  –  original draft. KHK: supervision, funding acquisition. JA: Planned and performed some of the litterbag experiments used here. MG: Performed the macrofossil analysis on the peat cores used in this study. All authors: writing  –  review and editing.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d2e7625">The contact author has declared that none of the authors has any competing interests.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d2e7631">Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this paper. The authors bear the ultimate responsibility for providing appropriate place names. Views expressed in the text are those of the authors and do not necessarily reflect the views of the publisher.</p>
  </notes><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d2e7637">This research has been supported by the Deutsche Forschungsgemeinschaft (grant nos. KN 929/23-1 and PE 1632/18-1).  This open-access publication was funded by the University of Münster.</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d2e7646">This paper was edited by Petr Kuneš and reviewed by two anonymous referees.</p>
  </notes><ref-list>
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