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<article xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:oasis="http://docs.oasis-open.org/ns/oasis-exchange/table" xml:lang="en" dtd-version="3.0" article-type="research-article"><?xmltex \bartext{Research article}?>
  <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-19-2881-2022</article-id><title-group><article-title>Origin, transport, and retention of fluvial sedimentary organic matter in South Africa's largest freshwater wetland,<?xmltex \hack{\break}?> Mkhuze Wetland System</article-title><alt-title>Origin and transport of Mkhuze sedimentary OM</alt-title>
      </title-group><?xmltex \runningtitle{Origin and transport of Mkhuze sedimentary OM}?><?xmltex \runningauthor{J. Gensel et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Gensel</surname><given-names>Julia</given-names></name>
          <email>julia.gensel@mail.de</email>
        <ext-link>https://orcid.org/0000-0002-8948-2231</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Humphries</surname><given-names>Marc Steven</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-4047-1451</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Zabel</surname><given-names>Matthias</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3 aff4">
          <name><surname>Sebag</surname><given-names>David</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-6446-6921</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Hahn</surname><given-names>Annette</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-3647-473X</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Schefuß</surname><given-names>Enno</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-5960-930X</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>MARUM – Center for Marine Environmental Sciences, University
of Bremen, Bremen, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>School of Chemistry, University of the Witwatersrand,
Johannesburg, South Africa</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>IFP Energies Nouvelles, Earth Sciences and Environmental Technologies Division, 92852 Rueil-Malmaison, France</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>University of Rouen Normandy, UNIROUEN, UNICAEN, CNRS, M2C, 76000 Rouen, France</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Julia Gensel (julia.gensel@mail.de)</corresp></author-notes><pub-date><day>13</day><month>June</month><year>2022</year></pub-date>
      
      <volume>19</volume>
      <issue>11</issue>
      <fpage>2881</fpage><lpage>2902</lpage>
      <history>
        <date date-type="received"><day>30</day><month>June</month><year>2021</year></date>
           <date date-type="rev-request"><day>7</day><month>July</month><year>2021</year></date>
           <date date-type="rev-recd"><day>31</day><month>March</month><year>2022</year></date>
           <date date-type="accepted"><day>4</day><month>April</month><year>2022</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2022 Julia Gensel et al.</copyright-statement>
        <copyright-year>2022</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/19/2881/2022/bg-19-2881-2022.html">This article is available from https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022.html</self-uri><self-uri xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022.pdf">The full text article is available as a PDF file from https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022.pdf</self-uri>
      <abstract><title>Abstract</title>

      <p id="d1e150">Sedimentary organic matter (OM) analyses along a 130 km long transect of the Mkhuze River from the Lebombo Mountains to its outlet into Lake St Lucia, Africa's most extensive estuarine system, revealed the present active trapping function of a terminal freshwater wetland. Combining bulk OM analyses, such as Rock-Eval<sup>®</sup>, and source-specific biomarker analyses of plant-wax <italic>n</italic>-alkanes and their stable carbon (<inline-formula><mml:math id="M1" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) and hydrogen (<inline-formula><mml:math id="M2" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D) isotopic composition showed that fluvial sedimentary OM originating from inland areas is mainly deposited in the floodplain and swamp area of the wetland system but not in the downstream lake area. A distinctly less degraded OM signature, i.e., a considerably lower degree of transformation of unstable components (higher <inline-formula><mml:math id="M3" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index) and lower contribution of refractory and persistent fractions (lower <inline-formula><mml:math id="M4" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index) as well as recognizably higher <inline-formula><mml:math id="M5" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D values compared to samples from upstream sub-environments, characterizes surface sediments of Lake St Lucia. The offset in <inline-formula><mml:math id="M6" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D indicates that the contributing vegetation, although similar to upstream vegetation inputs in terms of photosynthetic pathway (<inline-formula><mml:math id="M7" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) and alkane distribution pattern, experienced different hydrological growth conditions. The results suggest that under current conditions hinterland sedimentary OM is deposited throughout the wetland system up to the Mkhuze Swamps, which ultimately captures the transported OM. Consequently, samples from the downstream located Lake St Lucia show locally derived signals instead of integrated signals encompassing the river catchment. This finding raises important constraints for future environmental studies as the assumption of watershed-integrated signals in sedimentary archives retrieved from downstream lakes or offshore might not hold true in certain settings.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e226">Lake St Lucia is the largest estuarine system in Africa and is of both local and international importance <xref ref-type="bibr" rid="bib1.bibx64" id="paren.1"/>. It is a biodiversity hotspot and provides habitat for fish and wildlife and breeding grounds for birds. On this basis, it significantly supports national and international ecotourism as well as the regional economy <xref ref-type="bibr" rid="bib1.bibx96" id="paren.2"/>. Its functioning is highly dependent on a constant supply of freshwater. One of the major hydrological inputs into Lake St Lucia is the Mkhuze Wetland System, South Africa's largest freshwater wetland system, which accounts for about 56 % of the freshwater input to the lake <xref ref-type="bibr" rid="bib1.bibx81" id="paren.3"/>. It is part of the iSimangaliso Wetland Park, which was declared a UNESCO World Heritage Site in 1999 <xref ref-type="bibr" rid="bib1.bibx83" id="paren.4"/>, was designated a Ramsar site in 1986 <xref ref-type="bibr" rid="bib1.bibx62" id="paren.5"/>, and is the world's oldest formally protected estuary <xref ref-type="bibr" rid="bib1.bibx96" id="paren.6"/>.</p>
      <p id="d1e248">Wetlands act as filters by removing or retaining nutrients and anthropogenic pollutants <xref ref-type="bibr" rid="bib1.bibx69" id="paren.7"/>. They also control sedimentation through deposition, resulting in less siltation in adjacent water systems <xref ref-type="bibr" rid="bib1.bibx48" id="paren.8"/>. The filtering function of wetlands is of particular interest because wetlands are considered to be either sources or sinks of organic carbon and therefore may increase carbon emissions from surface waters if they export organic carbon (OC) in substantial amounts to adjacent water systems and vice versa <xref ref-type="bibr" rid="bib1.bibx14 bib1.bibx70 bib1.bibx60" id="paren.9"><named-content content-type="pre">e.g., </named-content></xref>. Factors controlling whether a wetland serves as a carbon source or sink are not yet fully understood, but wetland hydrology is considered to play a critical role. When a wetland's natural filter function is overstressed, the wetland and its beneficial functions can be reduced or destroyed <xref ref-type="bibr" rid="bib1.bibx36 bib1.bibx49" id="paren.10"/>. In the worst case, the wetland can become a source of pollutants and sediments that have been previously stored. The Mkhuze Wetland System, and in particular the Mkhuze Swamps, is supposedly such a filter for Lake St Lucia's water supply and therefore presumably provide the benefits mentioned above.</p>
      <p id="d1e265">Like most wetlands, the Mkhuze Wetland System is affected by human interference. For instance, cattle grazing and use as agricultural land are reported to be of increasing importance for both sugarcane and eucalyptus cultivation <xref ref-type="bibr" rid="bib1.bibx61" id="paren.11"/>. Human activities such as channel dredging (Mpempe and Tshanetshe canals) have also significantly altered the natural state <xref ref-type="bibr" rid="bib1.bibx61 bib1.bibx7 bib1.bibx24" id="paren.12"/>. Such
disturbances have the potential to cause alteration of vegetation and hydrologic conditions, as well as sediment balance and transport pathways. Such negative impacts have extensively been studied for the swamp system formerly present to the south of Lake St Lucia, the Mfolozi Swamps <xref ref-type="bibr" rid="bib1.bibx96 bib1.bibx87" id="paren.13"><named-content content-type="post">and references therein</named-content></xref>.</p>
      <p id="d1e279">Our study is, to the best of our knowledge, the first to examine the sources, transport, and fate of organic material in the Mkhuze Wetland System. The primary objectives of the study are (i) to characterize the sedimentary OM in the individual sub-areas of the system and (ii) to infer OM sources and transport as well as degradation of OM within the system. We, therefore, assume that rivers transport sedimentary material (if so) only downstream. In this context, signals observed in downstream areas can only originate from upstream areas through transport or from local sources. Thereby, we evaluate the current wetland's impact, especially of the Mkhuze Swamps on Lake St Lucia. To address the wetland's role in retaining sedimentary OM, we analyzed surface sediments along a 130 km long transect from the Mkhuze River channel to its mouth in Lake St Lucia, as well as extending into the northern part of Lake St Lucia.</p>
      <p id="d1e283">The provided insights into the characteristics and transport of organic matter in a terminal wetland under subtropical climatic conditions, which also can be identified in other wetlands around the world, reveal potential implications for (paleo)environmental studies based on sedimentary archives from downstream areas.</p><?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Approach and methodological background</title>
      <p id="d1e295">To obtain qualitative information on OM characteristics, we applied a combination of methods. Bulk methods (bulk organic and Rock-Eval<sup>®</sup> analyses) characterize the entire OM and its degradation state but are limited in their specificity, whereas compound-specific analyses, such as the identification of lipid biomarkers (i.e., plant-wax-derived <italic>n</italic>-alkanes) and their compound-specific isotope composition, provide very specific information but reflect only a small proportion of OM.</p>
<sec id="Ch1.S2.SS1">
  <label>2.1</label><title>Rock-Eval</title>
      <p id="d1e311">Originally developed to provide information on the content of hydrocarbons and the kerogen type in sedimentary rocks, as well as determine the maturity of the kerogen <xref ref-type="bibr" rid="bib1.bibx21 bib1.bibx52" id="paren.14"/>, Rock-Eval analysis has become an attractive and fast alternative for the analysis of organic matter in soils and sediments compared to conventional methods due to the lack of sample preparation <xref ref-type="bibr" rid="bib1.bibx22 bib1.bibx77" id="paren.15"/>. Rock-Eval analysis provides not only the quantity of organic carbon but also information on the elemental composition of the OM. In particular, the hydrogen index (HI; milligrams of <inline-formula><mml:math id="M8" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC) and oxygen index (OI; milligrams of <inline-formula><mml:math id="M9" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> per gram of TOC), which correlate with the classical elemental parameters of the <inline-formula><mml:math id="M10" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">H</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M11" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratios known from van Krevelen diagrams <xref ref-type="bibr" rid="bib1.bibx26 bib1.bibx28" id="paren.16"/>, not only provide insights into the degree of degradation but also provide indications of OM origin. The representation of the HI against TOC allows the estimation of the soil OM quality, which is usually determined by the mineralization of the soil OM and the dilution by the mineral matrix. Fresh and fragmented litter usually shows high TOC levels (10 %–40 %) and HI values greater than 300 <xref ref-type="bibr" rid="bib1.bibx22" id="paren.17"/>. This results from the material consisting primarily of unconverted biopolymers such as lignin, cellulose, and hemicellulose. During degradation (oxidation) of the biopolymers, the HI decreases and the OI increases. Material consisting of a distinct composition of the dominant biopolymers, such as aquatic inputs, likewise shows distinct ranges of its HI values, which provide a rough source indication.</p>
      <p id="d1e370">In addition, Rock-Eval provides information on the thermal stability of the immature OM <xref ref-type="bibr" rid="bib1.bibx20" id="paren.18"/>. The so-called S2 peak integrates the quantity of pyrolyzed emission products between 200 and 650 <inline-formula><mml:math id="M12" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. Utilizing mathematical deconvolution determines individual peaks within the S2 peak. Fractions of OM differing in thermal stability are assignable to the resulting temperature intervals: (A1) 200–340 <inline-formula><mml:math id="M13" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, thermally unstable biological macromolecules, like saccharides; (A2) 340–400 <inline-formula><mml:math id="M14" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, stable biological macromolecules, like cellulose and/or lignin or polypeptides; (A3) 400–460 <inline-formula><mml:math id="M15" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, immature geological macromolecules, like humic substances; (A4) 460–520 <inline-formula><mml:math id="M16" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, refractory geological macromolecules; and (A5) 520–650 <inline-formula><mml:math id="M17" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, highly refractory pool <xref ref-type="bibr" rid="bib1.bibx22 bib1.bibx77 bib1.bibx78" id="paren.19"/>. Investigations of composts using <inline-formula><mml:math id="M18" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:math></inline-formula>C nuclear magnetic resonance (NMR) showed that the thermal stability separating the mentioned groups also correlates with the chemical stability <xref ref-type="bibr" rid="bib1.bibx1" id="paren.20"/>. Based on this, <xref ref-type="bibr" rid="bib1.bibx77" id="text.21"/> and <xref ref-type="bibr" rid="bib1.bibx1" id="text.22"/> developed indices based on the aforementioned temperature intervals, whereby the indices are defined as follows: <inline-formula><mml:math id="M19" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index (<inline-formula><mml:math id="M20" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> is recalcitrant OM) <inline-formula><mml:math id="M21" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> (A3 <inline-formula><mml:math id="M22" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> A4 <inline-formula><mml:math id="M23" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> A5)<inline-formula><mml:math id="M24" display="inline"><mml:mrow><mml:mo>/</mml:mo><mml:mn mathvariant="normal">100</mml:mn></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M25" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index (<inline-formula><mml:math id="M26" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> is immature OM) <inline-formula><mml:math id="M27" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> log<inline-formula><mml:math id="M28" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">10</mml:mn></mml:msub></mml:math></inline-formula>((A1 <inline-formula><mml:math id="M29" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> A2)<inline-formula><mml:math id="M30" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula>A3). However, <xref ref-type="bibr" rid="bib1.bibx78" id="text.23"/> point out that due to their mathematical derivation, these indices cannot exactly indicate the quantity or identity of the chemical components in the OM, unlike the classic Rock-Eval parameters. We acknowledge that the four different temperature intervals cannot differentiate the entire spectrum of organic compounds and therefore refer to the thermal rather than chemical stability of OM <xref ref-type="bibr" rid="bib1.bibx78" id="paren.24"/>. Nevertheless, this sufficiently reflects the changes in the organic components during their transformation. On this basis, the <inline-formula><mml:math id="M31" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index and the <inline-formula><mml:math id="M32" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index describe the contribution of refractory and persistent fractions by pedogenic processes, as well as the degree of transformation of unstable components via decompositional processes <xref ref-type="bibr" rid="bib1.bibx78" id="paren.25"/>. <xref ref-type="bibr" rid="bib1.bibx78" id="text.26"/> proposed the use of the <inline-formula><mml:math id="M33" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram (<inline-formula><mml:math id="M34" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index vs. <inline-formula><mml:math id="M35" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index), which resembles the representation of the van Krevelen diagram (OI vs. HI). One of the most notable features of the <inline-formula><mml:math id="M36" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram is the linear relationship between the two parameters (“decomposition regression line” or “humic trend”). During the decomposition of fresh OM, labile organic compounds are converted into their respective more stable counterparts, which are converted into either stable humic acids or components complexed by the mineral matrix. Samples are plotted along the linear relationship when the stabilization of OM from the progressive degradation of organic components is based on their biochemical stability. Samples are not plotted along this linear relationship in situations with OM mixture from different sources.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <label>2.2</label><title>Plant waxes</title>
      <p id="d1e617">In general, lipid biomarkers reflect only a small portion of the total OM but overcome problems of source specificity by having a specific origin. Plants, for instance, produce waxes to control their water balance and counteract external stressors, such as UV radiation and bacterial and fungus-based attacks <xref ref-type="bibr" rid="bib1.bibx47" id="paren.27"/>. These waxes enter the environment through physical processes, such as wind, precipitation, abrasion by particles, and when plants die or plant parts detach. The waxes contain a variety of molecules, including long-chain <italic>n</italic>-alkanes, which are very resistant to degradation <xref ref-type="bibr" rid="bib1.bibx66" id="paren.28"/>. Plant-wax-derived <italic>n</italic>-alkanes show homologous series with a strong odd-over-even chain-length dominance due to their biosynthesis <xref ref-type="bibr" rid="bib1.bibx23" id="paren.29"/> causing a high carbon preference index (CPI) for fresh plant waxes. Besides, different plant types show characteristic features in their <italic>n</italic>-alkane distribution patterns, such as aquatic plants showing dominant contributions of the <italic>n</italic>-alkanes C<inline-formula><mml:math id="M37" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M38" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx5 bib1.bibx53" id="paren.30"/>, whereas grasses show distribution patterns dominated by the very long-chain <italic>n</italic>-alkanes C<inline-formula><mml:math id="M39" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M40" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula> as well as C<inline-formula><mml:math id="M41" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx71 bib1.bibx92" id="paren.31"/>. The differing abundances and dominance of the “higher-plant” <italic>n</italic>-alkanes are generally resembled in the ACL (average chain length) parameter <xref ref-type="bibr" rid="bib1.bibx65" id="paren.32"/>. The homologues C<inline-formula><mml:math id="M42" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M43" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">27</mml:mn></mml:msub></mml:math></inline-formula> seem to be mainly derived from tree-like vegetation <xref ref-type="bibr" rid="bib1.bibx91 bib1.bibx30 bib1.bibx98" id="paren.33"/>. However, both the C<inline-formula><mml:math id="M44" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> and the C<inline-formula><mml:math id="M45" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane can reflect a mixed signal from trees and grasses. The distribution patterns of the contributing plant types are closely mirrored in topsoils <xref ref-type="bibr" rid="bib1.bibx13" id="paren.34"/>. However, some studies have identified limitations of this approach and question the validity of distinctions by distribution patterns alone <xref ref-type="bibr" rid="bib1.bibx12 bib1.bibx46" id="paren.35"><named-content content-type="pre">e.g.,</named-content></xref>. Therefore, it is recommended to combine the information derived from <italic>n</italic>-alkane distribution patterns with additional proxies, such as compound-specific isotopic compositions <xref ref-type="bibr" rid="bib1.bibx39 bib1.bibx37 bib1.bibx98" id="paren.36"><named-content content-type="pre">e.g.,</named-content></xref>.</p>
</sec>
<sec id="Ch1.S2.SS3">
  <label>2.3</label><title>Plant-wax compound-specific isotopes</title>
      <p id="d1e771">The carbon and hydrogen in plant-wax <italic>n</italic>-alkanes derive from the carbon and hydrogen source the plants utilize for biomass metabolism, i.e., inorganic carbon and water. The isotopic composition of <italic>n</italic>-alkanes thus allows interpretation of either the metabolic process during biosynthesis or effects influencing the isotopic composition of the respective carbon and hydrogen sources <xref ref-type="bibr" rid="bib1.bibx74 bib1.bibx80 bib1.bibx19" id="paren.37"/>.</p>
      <p id="d1e783">In the case of carbon, the effect of different photosynthetic metabolic pathways of different types of vegetation has the greatest influence on the compound-specific stable carbon (<inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) of <italic>n</italic>-alkanes. Information on contributing photosynthetic plant types can be obtained from their compound-specific <inline-formula><mml:math id="M47" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C isotope compositions <xref ref-type="bibr" rid="bib1.bibx19" id="paren.38"/>. Waxes from C<inline-formula><mml:math id="M48" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> vegetation are isotopically enriched in <inline-formula><mml:math id="M49" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:math></inline-formula>C relative to waxes from C<inline-formula><mml:math id="M50" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> plants due to more effective photosynthetic carbon (CO<inline-formula><mml:math id="M51" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) fixation <xref ref-type="bibr" rid="bib1.bibx15" id="paren.39"/>. Most tropical grasses are of C<inline-formula><mml:math id="M52" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> type, while all trees and shrubs are C<inline-formula><mml:math id="M53" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> plants. The occurrence of C<inline-formula><mml:math id="M54" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, i.e., <inline-formula><mml:math id="M55" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:math></inline-formula>C-enriched <italic>n</italic>-alkanes, in sediments has thus been attributed to contributions from grassy environments. However, plants from specific environments, such as specific Cyperaceae or Poaceae in swamps or salt-tolerant plants in saline settings, can also be of C<inline-formula><mml:math id="M56" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> type, complicating a simple interpretation of <inline-formula><mml:math id="M57" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C compositions <xref ref-type="bibr" rid="bib1.bibx75" id="paren.40"/>. A complication arises when CAM plants are present. CAM plants produce variable and intermediate <inline-formula><mml:math id="M58" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C compositions but occur only in specific environments, such as in the Succulent Karoo Biome along the west coast of South Africa <xref ref-type="bibr" rid="bib1.bibx13" id="paren.41"/>. The <inline-formula><mml:math id="M59" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C compositions of plant waxes also depend on environmental stress, such as water shortage. Under drought conditions, plants close their stomata to increase their water use efficiency, leading to <inline-formula><mml:math id="M60" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:math></inline-formula>C enrichment <xref ref-type="bibr" rid="bib1.bibx41" id="paren.42"/>. <inline-formula><mml:math id="M61" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C compositions of plant waxes should thus only be interpreted in conjunction with other parameters.</p>
      <p id="d1e966">The hydrogen isotope composition (<inline-formula><mml:math id="M62" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D) of plant waxes mainly depends on environmental controlling factors rather than biosynthetic mechanisms. The hydrogen that plants incorporate into their biomass originates from the water they absorb. The hydrogen isotope composition of this water mainly depends on the hydrogen isotope composition of precipitation and the hydrological status of the environment. Regarding the hydrogen isotope composition of rainfall, different effects can be distinguished <xref ref-type="bibr" rid="bib1.bibx31" id="paren.43"/>. The continental and altitude effects describe the isotopic depletion with progressive rainout when moisture travels inland or uphill. The temperature effect describes the isotopic depletion with lower condensation temperatures. For the Mkhuze system, these effects result in plant waxes being isotopically depleted in hydrogen when derived from more inland or mountainous regions, whereas temperature variations play a negligible role. In contrast, the amount effect has a large influence leading to depleted hydrogen isotope compositions of rainfall under high-precipitation regimes <xref ref-type="bibr" rid="bib1.bibx18" id="paren.44"/>. Wetter areas are thus characterized by more depleted hydrogen isotope compositions of plant waxes. The latter effect is amplified by secondary isotope effects due to evaporation and transpiration. Water in soils, lakes, rivers, and wetlands may be isotopically enriched due to evaporation while also leaf water used for biosynthesis of waters may become isotopically enriched due to transpiration <xref ref-type="bibr" rid="bib1.bibx50" id="paren.45"/>. Such isotopic enrichment due to evapotranspiration has, for instance, been observed in dry environments of South Africa <xref ref-type="bibr" rid="bib1.bibx38 bib1.bibx82" id="paren.46"/>. Additionally, a slight dependency of <inline-formula><mml:math id="M63" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D composition of waxes occurs for different plant types <xref ref-type="bibr" rid="bib1.bibx74" id="paren.47"/>. Disentangling all processes affecting the <inline-formula><mml:math id="M64" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D of plant waxes may not always be possible in specific environments. Nevertheless, in combination these primary and secondary effects give an indication of the hydrological status of the contributing vegetation, i.e., about the general humidity of environments, especially when considered in conjunction with other parameters, as is done in this study.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Material and methods</title>
<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>Study site</title>
      <p id="d1e1022">The Mkhuze Wetland System (27.8<inline-formula><mml:math id="M65" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> S, 32.5<inline-formula><mml:math id="M66" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> E; Fig. <xref ref-type="fig" rid="Ch1.F1"/>), South Africa's largest freshwater wetland system (<inline-formula><mml:math id="M67" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">450</mml:mn></mml:mrow></mml:math></inline-formula> km<inline-formula><mml:math id="M68" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula>), is located in the northeastern coastal region of South Africa in the KwaZulu-Natal province. It is bordered by the Lebombo Mountain Range to the west and the Indian Ocean to the east and forms a mosaic of wetland types, including swamp forests, grassy swamps, and open water (pans) <xref ref-type="bibr" rid="bib1.bibx81" id="paren.48"/>. This ecological heterogeneity and biotic diversity are of international conservation importance, and therefore the area is listed as a wetland of international importance by the Ramsar Convention.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><?xmltex \currentcnt{1}?><?xmltex \def\figurename{Figure}?><label>Figure 1</label><caption><p id="d1e1070">Map of the Mkhuze catchment area. White circles represent sampling locations, and colored areas refer to the assigned sub-environments. Important geologic features, including watercourses and major lakes or pans, are named.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f01.png"/>

        </fig>

<sec id="Ch1.S3.SS1.SSS1">
  <label>3.1.1</label><title>Hydrology, vegetation, and depositional sub-environments</title>
      <p id="d1e1086">Two major hydrologic inflows supply water to the Mkhuze Wetland System, the Mkhuze River and Manzimbomvu streams, through local runoff, direct precipitation, or groundwater inflow <xref ref-type="bibr" rid="bib1.bibx24" id="paren.49"/>. The major tributary is the Mkhuze River, which originates east of Vryheid (<inline-formula><mml:math id="M69" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">125</mml:mn></mml:mrow></mml:math></inline-formula> km inland) and drains a catchment area of about 5250 km<inline-formula><mml:math id="M70" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> (see Fig. <xref ref-type="fig" rid="Ch1.F2"/>) consisting mainly of Cretaceous–Quaternary-aged sedimentary cover of the coastal plain <xref ref-type="bibr" rid="bib1.bibx58" id="paren.50"/>. The perennial river is fed primarily by direct precipitation and is characterized by a mean annual discharge of about <inline-formula><mml:math id="M71" display="inline"><mml:mrow><mml:mn mathvariant="normal">211</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">6</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> to <inline-formula><mml:math id="M72" display="inline"><mml:mrow><mml:mn mathvariant="normal">326</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">6</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> m<inline-formula><mml:math id="M73" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx45" id="paren.51"/>. Water flow varies greatly seasonally and interannually but is generally highest during the austral summer months and lowest to nonexistent during the winter months <xref ref-type="bibr" rid="bib1.bibx58" id="paren.52"/>. The river drains sedimentary strata of the Dwyka, Ecca, and lower Beaufort groups (Karoo Supergroup), as well as Pongola granites and rhyolites in the Lebombo Mountains <xref ref-type="bibr" rid="bib1.bibx58" id="paren.53"/>. It transports comparatively high amounts of sediment dominated by fine kaolinitic clays originating from Pongola granites and  Karoo Supergroup sedimentary rocks <xref ref-type="bibr" rid="bib1.bibx58" id="paren.54"/>. The second hydrologic input is water from the groundwater-fed streams from the north (Manzimbomvu streams) <xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx7" id="paren.55"/>. Unlike discharge in the Mkhuze River, these streams are characterized by regular, persistent flow and transport negligible amounts of suspended sediment.
The Mkhuze Wetland System can be divided into various sub-environments reflecting different depositional and geomorphological characteristics, namely the upper reach, the floodplain, the Mkhuze Swamps, and the outlet to Lake St Lucia. The upper reach (Fig. <xref ref-type="fig" rid="Ch1.F1"/>, red color) is the section extending from east of the Lebombo Mountain Range to Nsumo Pan. It is dominated by trees, such as <italic>Acacia xanthophloea</italic> and <italic>Ficus sycomorus</italic>, along the river course <xref ref-type="bibr" rid="bib1.bibx85" id="paren.56"/>. The Mkhuze River in this area is a degrading river being largely confined to its channel <xref ref-type="bibr" rid="bib1.bibx3" id="paren.57"/>. Farther downstream, the river traverses a sandy coastal plain where it forms an extensive floodplain (Fig. <xref ref-type="fig" rid="Ch1.F1"/>, orange color) which is characterized by a variety of vegetation communities (<italic>Phragmites mauritianus</italic> reed swamp community, <italic>Imperata cylindrica</italic> hygrophilous grassland community, <italic>Echinochloa pyramidalis</italic> backswamp community, <italic>Ficus sycomorus</italic> riparian forest community distributed along the Mkhuze River, <italic>Cynodon dactylon</italic> floodplain community, <italic>Acacia xanthophloea</italic> woodland community, and the <italic>Nymphaea</italic> sp. aquatic community; <xref ref-type="bibr" rid="bib1.bibx88 bib1.bibx61" id="altparen.58"/>; Fig. <xref ref-type="fig" rid="Ch1.F3"/>) and is partly used for agricultural purposes. During periods of high flow, the Mkhuze River overtops its banks and inundates the floodplain <xref ref-type="bibr" rid="bib1.bibx2" id="paren.59"/>. Flooding results in sediment deposition in the immediate vicinity of the channel due to slower flow velocity caused by riparian vegetation, resulting in the formation of natural levees <xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx61 bib1.bibx25" id="paren.60"/>, as well as the recharge of pans located in the north–south-oriented fossil dune system. As a result, the Mkhuze River is a highly dynamic and rapidly aggrading system, characterized by relatively high sedimentation rates <xref ref-type="bibr" rid="bib1.bibx43" id="paren.61"><named-content content-type="pre">0.25–0.50 cm yr<inline-formula><mml:math id="M74" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>;</named-content></xref>. Loss of water to the surrounding floodplain results in marked reductions in downstream channel size, and the Mkhuze River gradually loses definition before terminating in a large freshwater swamp, termed the Mkhuze Swamps (Fig. <xref ref-type="fig" rid="Ch1.F1"/>, green color). The Mkhuze Swamps function as an intermediate reservoir that fills with water during the summer and releases it into Lake St Lucia (Fig. <xref ref-type="fig" rid="Ch1.F1"/>, blue color) from the beginning of the dry season when the lake is no longer primarily fed by direct precipitation <xref ref-type="bibr" rid="bib1.bibx2 bib1.bibx85" id="paren.62"/>. Dominant vegetation of the Mkhuze Swamps includes <italic>Cyperus papyrus</italic>, <italic>Phragmites mauritianus</italic>, and <italic>Echinochloa pyramidalis</italic> <xref ref-type="bibr" rid="bib1.bibx85" id="paren.63"/>. On the levees <italic>Ficus sycomorus</italic> and <italic>Ficus trichopoda</italic> occur, whereas the pans are characterized by <italic>Nymphaea</italic> sp. <xref ref-type="bibr" rid="bib1.bibx85" id="paren.64"/>. In the northern parts of Lake St Lucia nearly monospecific stands of the salt-tolerant <italic>Sporobolus virginicus</italic> can be found <xref ref-type="bibr" rid="bib1.bibx81" id="paren.65"/>. Because Lake St Lucia is an extremely shallow lake (average depth <inline-formula><mml:math id="M75" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> m), it is highly susceptible to evaporative losses <xref ref-type="bibr" rid="bib1.bibx45" id="paren.66"><named-content content-type="pre"><inline-formula><mml:math id="M76" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">1380</mml:mn></mml:mrow></mml:math></inline-formula> mm yr<inline-formula><mml:math id="M77" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>;</named-content></xref> and dependent on constant water supply from the swamp system.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><?xmltex \currentcnt{2}?><?xmltex \def\figurename{Figure}?><label>Figure 2</label><caption><p id="d1e1317">The vegetation coverage in the surroundings of the Mkhuze Wetland System is shown. The figure displays the entire catchment area of the Mkhuze River (represented by the outlined, lightened area). The red rectangle indicates the extent of the study area (see Fig. <xref ref-type="fig" rid="Ch1.F1"/>). In addition to vegetation cover, precipitation isolines (left figure) and evaporation isolines (right figure, in mm yr<inline-formula><mml:math id="M78" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>) are overlaid <xref ref-type="bibr" rid="bib1.bibx84" id="paren.67"><named-content content-type="pre">adopted from</named-content></xref>.</p></caption>
            <?xmltex \igopts{width=483.69685pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f02.png"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3" specific-use="star"><?xmltex \currentcnt{3}?><?xmltex \def\figurename{Figure}?><label>Figure 3</label><caption><p id="d1e1347">Distribution in the vegetation communities and land use on the Mkhuze Floodplain in 1937 (left) and 1996 (right) <xref ref-type="bibr" rid="bib1.bibx61" id="paren.68"><named-content content-type="pre">adopted from</named-content></xref>.</p></caption>
            <?xmltex \igopts{width=483.69685pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f03.png"/>

          </fig>

</sec>
<sec id="Ch1.S3.SS1.SSS2">
  <label>3.1.2</label><title>Climate</title>
      <p id="d1e1370">The study area experiences a subtropical climate characterized by hot, humid summers and mild, dry winters and mean annual temperatures ranging from 21 to 23 <inline-formula><mml:math id="M79" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C <xref ref-type="bibr" rid="bib1.bibx68" id="paren.69"/>. The Mkhuze Wetland System lies within the summer rainfall zone of South Africa, with about 60 % of precipitation occurring during the austral summer  months (November through March) in association with cold fronts moving northward along the coast <xref ref-type="bibr" rid="bib1.bibx94" id="paren.70"/>. Precipitation gradually decreases from east to west <xref ref-type="bibr" rid="bib1.bibx90" id="paren.71"><named-content content-type="pre">see Fig. <xref ref-type="fig" rid="Ch1.F2"/>;</named-content></xref> from 1000 to 600 mm yr<inline-formula><mml:math id="M80" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx44 bib1.bibx57" id="paren.72"/>. Flooding is highly variable and usually associated with cutoff-low-pressure systems that develop during December and January or with infrequent tropical cyclones. Evapotranspiration rates are considered relatively high, ranging from 80 mm per month in winter to 190 mm per month in summer <xref ref-type="bibr" rid="bib1.bibx94" id="paren.73"/>.</p>
</sec>
<sec id="Ch1.S3.SS1.SSS3">
  <label>3.1.3</label><title>Anthropogenically caused changes</title>
      <p id="d1e1422">The course of the Mkhuze River has been greatly altered by human intervention, beginning in the early 1970s. A prolonged drought (1968–1971) resulted in hypersaline conditions in Lake St Lucia <xref ref-type="bibr" rid="bib1.bibx24" id="paren.74"/>. The authorities attempted to increase the freshwater supply to the lake by excavating a canal (Mpempe Canal from near Mpempe Pan to 1 km south of Demazane Pan) <xref ref-type="bibr" rid="bib1.bibx61" id="paren.75"/>. Flooding caused by Cyclone Domoina in 1984 resulted in severe erosion and the formation of a new stream between Tshanetshe Pan and Mpempe Pan <xref ref-type="bibr" rid="bib1.bibx86" id="paren.76"/>. Additional dredging of a channel (Tshanetshe Canal) in 1986 by a local farmer <xref ref-type="bibr" rid="bib1.bibx61" id="paren.77"/> resulted in the fact that today much of the Mkhuze River water is diverted through the Tshanetshe–Demazane Canal System <xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx61 bib1.bibx7 bib1.bibx24" id="paren.78"/>. Scientific evaluation of the actions taken and their consequences for the system has been overwhelmingly negative <xref ref-type="bibr" rid="bib1.bibx2 bib1.bibx85" id="paren.79"><named-content content-type="pre">e.g.,</named-content></xref>. However, <xref ref-type="bibr" rid="bib1.bibx24" id="text.80"/> not only provide a detailed description of the channelization processes in the Mkhuze Wetland System to which the reader is referred but also emphasize that the alteration of the Mkhuze River flow would also likely have occurred naturally. One aspect which is attributed to the channelization processes is a change in vegetation cover. It is reported that formerly extensive stands of <italic>Cyperus papyrus</italic> within the floodplain area were reduced in extension and partly replaced by species which are tolerant to frequent inundation instead of permanently flooded conditions, such as <italic>Cyperus natalensis</italic> and <italic>Echinochloa pyramidalis</italic> <xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx61" id="paren.81"/>.</p>
</sec>
</sec>
<sec id="Ch1.S3.SS2">
  <label>3.2</label><title>Sampling</title>
      <p id="d1e1470">Collection of samples took place during a single field campaign in November–December 2018. Ten plant samples were collected. If possible, replicate plant species were sampled at various sampling sites within the system. The different species were selected based on the occurrence of large cohorts in the field or based on high reported occurrences in previous studies (<xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx61" id="altparen.82"/>; see also Fig. <xref ref-type="fig" rid="Ch1.F3"/>), but not all major plant communities mentioned could successfully be sampled during the field campaign. Sampled species include aquatic plants from the Nymphaeaceae family (<inline-formula><mml:math id="M81" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula>) as well as the aquatic plant <italic>Phragmites australis</italic> (<inline-formula><mml:math id="M82" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula>) growing on both dry and flooded soils; two species of wetland grasses, namely <italic>Vossia cuspidata</italic> (<inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula>) and <italic>Cynodon dactylon</italic> (<inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula>); and two representatives of the Cyperaceae family, namely <italic>Cyperus papyrus</italic> (<inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>) and <italic>Cyperus alternifolius</italic> (<inline-formula><mml:math id="M86" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>). A total of 41 surface sediment samples (uppermost 10 cm) were collected along the course of the Mkhuze River and a transect extending into North Lake (northern part of Lake St Lucia, Fig. <xref ref-type="fig" rid="Ch1.F1"/>). The collection of sediment samples was conducted under permit from Ezemvelo KZN Wildlife and iSimangaliso Wetland Park Authority. Because of the limited number of samples due to the difficult accessibility of the sampling area, the results should be considered qualitatively rather than quantitatively.</p>
</sec>
<sec id="Ch1.S3.SS3">
  <label>3.3</label><title>Laboratory analyses</title>
      <p id="d1e1577">All surface sediments were freeze-dried. A sieved <?xmltex \hack{\mbox\bgroup}?>(<inline-formula><mml:math id="M87" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">212</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M88" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m)<?xmltex \hack{\egroup}?> sub-sample of approximately 100 mg was removed for classical bulk parameter analysis, and the residual sample was ground and sub-sampled for analyses. All glassware was combusted at 450 <inline-formula><mml:math id="M89" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for 5 h prior to use.</p>
<sec id="Ch1.S3.SS3.SSS1">
  <label>3.3.1</label><title>Bulk organic matter analyses</title>
      <p id="d1e1618">The dry, sieved surface sediment was re-wetted with Milli-Q water, and approximately 20 mL of hydrochloric acid (10 %) was added. After 12 h, the acidic solution was decanted and the sample was centrifuged at 1000 rpm for 5 min. The supernatant liquid was then removed with a pipette. The washing procedure was repeated (four to five times) until a pH of 5 was reached, and the decalcified sediment was freeze-dried. Bulk organic analyses for determining total carbon and nitrogen content and bulk carbon isotope signatures were performed at MARUM, University of Bremen. About 10 mg of decalcified samples was wrapped in a tin capsule and analyzed with an elemental analyzer (EA)–continuous-flow isotope ratio mass spectrometer (IRMS) (Thermo Finnigan Flash EA 2000 coupled to a Delta V Plus IRMS). The combustion oven (filled with quartz wool, chromium oxide, and silvered cobaltous–cobaltic oxide), in which C- and N-containing compounds are oxidized, was operated at 999 <inline-formula><mml:math id="M90" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. This was followed by reduction of the resulting nitrogen gases in the reduction reactor (filled with quartz wool and copper-reduced granulate) operated at 680 <inline-formula><mml:math id="M91" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. Water formed was removed in a water trap (filled with magnesium perchlorate). Finally, N<inline-formula><mml:math id="M92" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and CO<inline-formula><mml:math id="M93" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> were separated chromatographically (using an IRMS steel separation column for NC; length 300 cm, o.d. 6 mm, i.d. 5 mm, kept at 40 <inline-formula><mml:math id="M94" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) and transferred on-line to the IRMS via a Conflow IV interface. Helium as carrier gas and oxygen as oxidation reagent were used at flow rates of 100 and 200 mL min<inline-formula><mml:math id="M95" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, respectively. Primary standardization of the Delta V Plus IRMS was based on duplicate injections of a reference gas standard from a laboratory tank. The CO<inline-formula><mml:math id="M96" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> reference gas (<inline-formula><mml:math id="M97" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C <inline-formula><mml:math id="M98" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 34.17 ‰ <inline-formula><mml:math id="M99" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1 ‰ vs. Vienna Pee Dee Belemnite (VPDB), 5.0 V <inline-formula><mml:math id="M100" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5 V at <inline-formula><mml:math id="M101" display="inline"><mml:mrow><mml:mi>m</mml:mi><mml:mo>/</mml:mo><mml:mi>z</mml:mi></mml:mrow></mml:math></inline-formula> 44) was calibrated using IAEA-CH-6 international standards. Quantification of total nitrogen and organic carbon was achieved by external standard calibration using peak areas that yielded a linear five-point calibration curve. Repeated analysis of an internal laboratory standard cross-referenced to the certified IAEA-CH-6 international standard yielded a precision and accuracy of 0.2 ‰ for each. Sample concentration data are reported blank corrected.</p>
      <p id="d1e1733">Thermal analyses were performed at the IFP Energies Nouvelles lab (Rueil-Malmaison, France) using a Rock-Eval<sup>®</sup> 6 device (Vinci Technologies). About 80 mg of freeze-dried ground sample was pyrolyzed in an inert atmosphere (N<inline-formula><mml:math id="M102" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>) by heating from 200 to 650 <inline-formula><mml:math id="M103" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C at 25 <inline-formula><mml:math id="M104" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C min<inline-formula><mml:math id="M105" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>; then residual carbon was combusted in air from 300 to 850 <inline-formula><mml:math id="M106" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C at 20 <inline-formula><mml:math id="M107" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C min<inline-formula><mml:math id="M108" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> <xref ref-type="bibr" rid="bib1.bibx27 bib1.bibx22" id="paren.83"/>. Gases released were monitored by a flame ionization detector (FID) for hydrocarbon (HC) compounds, and by infrared (IR) detectors for CO and CO<inline-formula><mml:math id="M109" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>. Total organic carbon (TOC in wt %), mineral carbon (MinC in wt %), the hydrogen index (HI in milligrams of HC per gram of TOC), and the oxygen index (OI in milligrams of <inline-formula><mml:math id="M110" 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> per gram of TOC) were calculated by integrating the amounts of HC, CO, and CO<inline-formula><mml:math id="M111" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> produced during thermal cracking and combustion of OM or thermal decomposition of carbonates between defined temperature limits <xref ref-type="bibr" rid="bib1.bibx8 bib1.bibx52" id="paren.84"/>. Since cracking temperature of organic compounds depends on their structural stability, the thermal status of OM was characterized by combining the <inline-formula><mml:math id="M112" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index (i.e., relative contribution of most thermally stable HC pools) and <inline-formula><mml:math id="M113" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index <xref ref-type="bibr" rid="bib1.bibx78" id="paren.85"><named-content content-type="pre">i.e., ratio between thermally labile and resistant HC pools; details are in</named-content></xref>. As it is derived from a mathematical construct, if the gradual decomposition of labile compounds is its main driver, OM composition can be described as a continuum from biological tissues to a mixture of organic constituents derived from OM decomposition and plotted along a linear regression line <xref ref-type="bibr" rid="bib1.bibx56" id="paren.86"><named-content content-type="pre">called the “decomposition line”;</named-content></xref> in the diagram of the <inline-formula><mml:math id="M114" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index vs. <inline-formula><mml:math id="M115" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index <xref ref-type="bibr" rid="bib1.bibx1" id="paren.87"><named-content content-type="pre">called hereafter <inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram;</named-content></xref>. However, situations with OM mixture from different sources or where decomposition is so intense that it even affects the more thermally stable pools may generate a distribution diverging from the decomposition line. In addition, since decomposition temperature of carbonates depends on their composition, examination of CO<inline-formula><mml:math id="M117" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and CO thermograms enables us to identify the carbonate minerals present in the mineral matrix <xref ref-type="bibr" rid="bib1.bibx63 bib1.bibx79" id="paren.88"/>.</p>
</sec>
<sec id="Ch1.S3.SS3.SSS2">
  <label>3.3.2</label><?xmltex \opttitle{Determination of \textit{n}-alkane concentrations}?><title>Determination of <italic>n</italic>-alkane concentrations</title>
      <p id="d1e1925">Extraction of plant-wax-derived <italic>n</italic>-alkanes from surface sediments was carried out using a Dionex Accelerated Solvent Extractor 200 (three cycles – 5 min, 100 <inline-formula><mml:math id="M118" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, 1000 psi). The internal standard (ISTD) squalane was added prior to extraction. A mixture of dichloromethane and methanol (<inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M120" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>:</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) served as extraction solvent. Recovered total lipid extracts (TLEs) were desulfurized with activated copper for 12 h. Plant samples were cut into small pieces resembling all parts of the plant and extracted by using ultrasonic homogenizers and a sequence of methanol, dichloromethane <inline-formula><mml:math id="M121" display="inline"><mml:mo>:</mml:mo></mml:math></inline-formula> methanol (<inline-formula><mml:math id="M122" display="inline"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>:</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>), and dichloromethane as extraction solvents (5 min each at room temperature). Solvents were combined, and the ISTD was added. Saponification of all TLEs was carried out using 0.1 M potassium hydroxide solution in methanol : water (<inline-formula><mml:math id="M124" display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M125" display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>:</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) at 85 <inline-formula><mml:math id="M126" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C for 2 h, and neutral fractions were extracted with hexane. The apolar fraction was retrieved by column separation using deactivated silica (1 % H<inline-formula><mml:math id="M127" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O in hexane) and hexane followed by removal of unsaturated components via column chromatography on silver-nitrate-impregnated silica using hexane to yield the saturated hydrocarbon fraction.</p>
      <p id="d1e2038">Analyses were performed using a FOCUS gas chromatograph coupled to a flame ionization detector (GC-FID). The GC oven hosted a Restek Rxi-5ms capillary column (30 m <inline-formula><mml:math id="M128" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 250 <inline-formula><mml:math id="M129" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m <inline-formula><mml:math id="M130" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 0.25 <inline-formula><mml:math id="M131" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m). The inlet temperature was set to 260 <inline-formula><mml:math id="M132" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, and splitless injection mode was used. The GC oven was set at 60 <inline-formula><mml:math id="M133" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, held for 2 min, increased to 150 <inline-formula><mml:math id="M134" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C with a heating rate of 20 <inline-formula><mml:math id="M135" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C min<inline-formula><mml:math id="M136" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, and subsequently followed by an increase of 4 <inline-formula><mml:math id="M137" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C min<inline-formula><mml:math id="M138" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> to the final temperature of 320 <inline-formula><mml:math id="M139" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, which was held for 11 min. Quantification of the long-chain <italic>n</italic>-alkanes was performed by external standard calibration using the peak areas. The external standard used for this purpose contains <italic>n</italic>-alkanes (C<inline-formula><mml:math id="M140" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">19</mml:mn></mml:msub></mml:math></inline-formula> to C<inline-formula><mml:math id="M141" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">34</mml:mn></mml:msub></mml:math></inline-formula>) at a concentration of 10 ng <inline-formula><mml:math id="M142" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>L<inline-formula><mml:math id="M143" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> each and was measured repeatedly after all six samples, achieving a relative standard deviation of <inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">9.2</mml:mn></mml:mrow></mml:math></inline-formula> %. A blank sample containing only the internal standard (ISTD) and a double blank sample not containing the ISTD were also measured to ensure that no contamination occurred during the sample preparation and measurement. Recovery of the ISTD was 74.6 % <inline-formula><mml:math id="M145" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 15.4 % on average for all samples and blanks.</p>
</sec>
<sec id="Ch1.S3.SS3.SSS3">
  <label>3.3.3</label><?xmltex \opttitle{Stable isotope analyses of \textit{n}-alkanes}?><title>Stable isotope analyses of <italic>n</italic>-alkanes</title>
      <p id="d1e2225">Compound-specific <inline-formula><mml:math id="M146" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C values of the long-chain <italic>n</italic>-alkanes were determined using a TRACE GC Ultra equipped with an Agilent HP-5ms capillary column (30 m <inline-formula><mml:math id="M147" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 250 <inline-formula><mml:math id="M148" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m <inline-formula><mml:math id="M149" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 0.25 <inline-formula><mml:math id="M150" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>m) coupled to a Finnigan MAT 252 IRMS via a combustion interface (operation at 1000 <inline-formula><mml:math id="M151" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C). The GC oven temperature was set at 120 <inline-formula><mml:math id="M152" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, held for 3 min, raised to the final temperature of 320 <inline-formula><mml:math id="M153" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C at a heating rate of 5 <inline-formula><mml:math id="M154" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C min<inline-formula><mml:math id="M155" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, and then held for 15 min. CO<inline-formula><mml:math id="M156" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> was used as the reference gas. All samples were measured in duplicate if sufficient material was available, and values are given in per mil VPDB. Standard deviations of replicate analyses of all odd-numbered <italic>n</italic>-alkanes analyzed (C<inline-formula><mml:math id="M157" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula> to C<inline-formula><mml:math id="M158" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>) were less than 0.25 ‰(C<inline-formula><mml:math id="M159" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub><mml:mo>,</mml:mo><mml:mn mathvariant="normal">0.10</mml:mn></mml:mrow></mml:math></inline-formula> ‰ <inline-formula><mml:math id="M160" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.07 ‰; C<inline-formula><mml:math id="M161" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula>, 0.07 ‰ <inline-formula><mml:math id="M162" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.05 ‰; C<inline-formula><mml:math id="M163" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">27</mml:mn></mml:msub></mml:math></inline-formula>, 0.08 ‰ <inline-formula><mml:math id="M164" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 ‰; C<inline-formula><mml:math id="M165" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula>, 0.06 ‰ <inline-formula><mml:math id="M166" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 ‰; C<inline-formula><mml:math id="M167" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula>, 0.09 ‰ <inline-formula><mml:math id="M168" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 ‰; C<inline-formula><mml:math id="M169" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula>, 0.07 ‰ <inline-formula><mml:math id="M170" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 ‰; C<inline-formula><mml:math id="M171" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>, 0.08 ‰ <inline-formula><mml:math id="M172" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 ‰). Accuracy and precision were determined by analyses of an external <italic>n</italic>-alkane standard calibrated against the A4-Mix isotope standard (Arndt Schimmelmann, Indiana University) and measured repetitively every six samples. The precision (% RSD) and accuracy (bias compared to the offline value determined via elemental analysis) of the internal standard (<inline-formula><mml:math id="M173" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M174" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mtext>squalane</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">19.9</mml:mn></mml:mrow></mml:math></inline-formula> ‰ <inline-formula><mml:math id="M175" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3 ‰) were 1.6 % and <inline-formula><mml:math id="M176" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.27‰, respectively.
Compound-specific stable hydrogen isotope <inline-formula><mml:math id="M177" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D values were determined using a TRACE GC Ultra (column and temperature program are the same as for <inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C) coupled to a Finnigan MAT 253 IRMS via a pyrolysis reactor (operating at 1420 <inline-formula><mml:math id="M179" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C). H<inline-formula><mml:math id="M180" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> was used as the reference gas, and all samples were measured as duplicates when sufficient sample volume was available. Reported values are in per mil Vienna Standard Mean Ocean Water (VSMOW). Standard deviations of replicate analyses of all <italic>n</italic>-alkanes analyzed (C<inline-formula><mml:math id="M181" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula> to C<inline-formula><mml:math id="M182" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>) were less than 3 ‰(C<inline-formula><mml:math id="M183" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula>, 1.0 ‰ <inline-formula><mml:math id="M184" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.59 ‰; C<inline-formula><mml:math id="M185" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">27</mml:mn></mml:msub></mml:math></inline-formula>, 1.08 ‰ <inline-formula><mml:math id="M186" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.67 ‰; C<inline-formula><mml:math id="M187" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula>, 0.49 ‰ <inline-formula><mml:math id="M188" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.54 ‰; C<inline-formula><mml:math id="M189" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula>, 0.46 ‰ <inline-formula><mml:math id="M190" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.46 ‰; C<inline-formula><mml:math id="M191" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula>, 0.62 ‰ <inline-formula><mml:math id="M192" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.46 ‰; C<inline-formula><mml:math id="M193" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>, 0.68 ‰ <inline-formula><mml:math id="M194" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.56 ‰). Accuracy and precision were determined by analyses of an external <italic>n</italic>-alkane standard calibrated against the A4-Mix isotope standard (Arndt Schimmelmann, Indiana University) measured repeatedly every six samples. The precision (% RSD) and accuracy (bias compared to the offline value) of the internal standard (<inline-formula><mml:math id="M195" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D<inline-formula><mml:math id="M196" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mtext>squalane</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">180</mml:mn></mml:mrow></mml:math></inline-formula> ‰ <inline-formula><mml:math id="M197" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3 ‰) were 1.4 % and 0.03 ‰, respectively. The H<inline-formula><mml:math id="M198" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> factor was repeatedly measured and gave a value of 4.8 <inline-formula><mml:math id="M199" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1 over the whole measurement series.</p><?xmltex \hack{\newpage}?>
</sec>
</sec>
<sec id="Ch1.S3.SS4">
  <label>3.4</label><?xmltex \opttitle{Distributional parameters of \textit{n}-alkanes}?><title>Distributional parameters of <italic>n</italic>-alkanes</title>
      <p id="d1e2736">The carbon preference index (CPI) and the average chain length (ACL) were adapted from <xref ref-type="bibr" rid="bib1.bibx17" id="text.89"/> and <xref ref-type="bibr" rid="bib1.bibx65" id="text.90"/>, respectively. The following calculations were made: <?xmltex \hack{\\}?><italic>Carbon preference index.</italic>
            <disp-formula id="Ch1.E1" content-type="numbered"><label>1</label><mml:math id="M200" display="block"><mml:mrow><mml:mi mathvariant="normal">CPI</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.5</mml:mn><mml:mo>×</mml:mo><mml:mfenced close="]" open="["><mml:mrow><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mn mathvariant="normal">23</mml:mn><mml:mn mathvariant="normal">33</mml:mn></mml:msubsup><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">odd</mml:mi></mml:msub></mml:mrow><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mn mathvariant="normal">22</mml:mn><mml:mn mathvariant="normal">32</mml:mn></mml:msubsup><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">even</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>+</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mn mathvariant="normal">25</mml:mn><mml:mn mathvariant="normal">35</mml:mn></mml:msubsup><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">odd</mml:mi></mml:msub></mml:mrow><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mn mathvariant="normal">24</mml:mn><mml:mn mathvariant="normal">34</mml:mn></mml:msubsup><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">even</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mfenced><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
          <italic>Average chain length.</italic>
            <disp-formula id="Ch1.E2" content-type="numbered"><label>2</label><mml:math id="M201" display="block"><mml:mrow><mml:mi mathvariant="normal">ACL</mml:mi><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mn mathvariant="normal">23</mml:mn><mml:mn mathvariant="normal">35</mml:mn></mml:msubsup><mml:mi>i</mml:mi><mml:mo>×</mml:mo><mml:msub><mml:mi>C</mml:mi><mml:mtext>i, odd</mml:mtext></mml:msub></mml:mrow><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mn mathvariant="normal">23</mml:mn><mml:mn mathvariant="normal">35</mml:mn></mml:msubsup><mml:msub><mml:mi>C</mml:mi><mml:mtext>i, odd</mml:mtext></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
          <italic>Relative concentration (contribution) [%].</italic>
            <disp-formula id="Ch1.E3" content-type="numbered"><label>3</label><mml:math id="M202" display="block"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow><mml:mrow><mml:msubsup><mml:mo>∑</mml:mo><mml:mn mathvariant="normal">23</mml:mn><mml:mn mathvariant="normal">35</mml:mn></mml:msubsup><mml:msub><mml:mi>C</mml:mi><mml:mtext>even, odd</mml:mtext></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
</sec>
<sec id="Ch1.S3.SS5">
  <label>3.5</label><title>Statistical analyses</title>
      <p id="d1e2920">All statistical analyses were performed using R software (R version 4.0.3 and RStudio version 1.4.1103). To test whether statistically significant differences occurred between the sub-environments, the Kruskal–Wallis test was performed using the stat_cor_mean() function of the “ggpubr” package (version 0.4.0). When the <italic>p</italic> value indicated that differences (<inline-formula><mml:math id="M203" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>) between sub-environments were evident, the test was supplemented with a pairwise Wilcoxon rank sum test (base package “stats”) to determine which sub-environments had significant differences between them. The Benjamini and Hochberg “BH” method was used to adjust <inline-formula><mml:math id="M204" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> values. Correlation coefficients were calculated by using the  stat_cor function with the default Pearson method of the ggpubr package (version 0.4.0). Box-and-whisker plots were generated using the “ggplot2” system (version 2.3.3.3) of the “tidyverse” package (version 1.3.0) and ggpubr (version 0.4.0) and the geom_boxplot() function implemented here. Here, the median of the respective data is shown as a solid line and the lower and upper hinges correspond to the first (25th percentile) and third (75th percentile) quartiles. The lower/upper whisker extends from the lower/upper hinge to the smallest/largest value if it is not smaller/larger than 1.5 times the interquartile range from the hinge. Otherwise, the respective data point is drawn as a single point representing an outlier. For the principal component analysis (PCA) performed, missing values of the data set were first imputed using the impute.PCA() function and applying the regularized iterative PCA algorithm of the “missMDA” package (version 1.18). Subsequently, the actual PCA calculations were performed by using the prcomp() function (base package stats).</p><?xmltex \hack{\newpage}?>
</sec>
</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Results</title>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><title>Chemical parameters of bulk organic matter</title>
      <p id="d1e2962">Total organic carbon (TOC), as a measure of organic matter (OM) content, increased in surface sediments from the upper reach to the swamp sub-environment, where samples contained the highest amounts of TOC, ranging from 0.9 % to 8.1 % (Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>). Higher variance is observed for the upper reach, floodplain, and swamp sub-environment, compared to very narrow ranges of values in the delta (1.4 %–1.8 %) and lake sub-environment (1.4 %–1.7 %). Samples from the floodplain and swamp sub-environments show significantly higher <inline-formula><mml:math id="M205" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula> ratios compared to the other sub-environments (<inline-formula><mml:math id="M206" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>, Table <xref ref-type="table" rid="Ch1.T1"/>). To estimate the total amount of plant-wax input to the sub-environments, the sum of the concentrations of all long-chain odd-numbered <italic>n</italic>-alkanes was considered (Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>). When normalized to sample mass, delta and lake samples contained significantly lower amounts of plant-wax-derived lipids compared to swamp samples (<inline-formula><mml:math id="M207" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.005</mml:mn></mml:mrow></mml:math></inline-formula>). However, when normalized to organic carbon, no significant differences were detected between any of the sub-environments investigated (<inline-formula><mml:math id="M208" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>). Bulk OM <inline-formula><mml:math id="M209" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C shows more depleted values in the samples from the upper reach and the swamp sub-environments than in the other sub-environments, but statistical evidence is present only for the distinction between the swamp sub-environment on the one hand and the delta and lake sub-environments on the other (<inline-formula><mml:math id="M210" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>).</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><?xmltex \currentcnt{1}?><label>Table 1</label><caption><p id="d1e3054">Chemical parameters of sedimentary bulk organic matter: total organic carbon content (TOC) in % dry weight (DW), carbon-to-nitrogen ratio (<inline-formula><mml:math id="M211" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula>), summed concentration of medium to very long-chain plant-wax-derived <italic>n</italic>-alkanes normalized to dry weight, and organic carbon (OC), and bulk organic carbon isotopic composition in per mil in reference to Vienna Pee Dee Belemnite.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="8">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1">Sub-environment</oasis:entry>
         <oasis:entry colname="col2">TOC</oasis:entry>
         <oasis:entry colname="col3"><inline-formula><mml:math id="M212" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M213" display="inline"><mml:mrow><mml:mo>∑</mml:mo><mml:msub><mml:mi mathvariant="normal">conc</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">22</mml:mn></mml:msub></mml:mrow><mml:mo>-</mml:mo><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:mrow></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M214" display="inline"><mml:mrow><mml:mo>∑</mml:mo><mml:msub><mml:mi mathvariant="normal">conc</mml:mi><mml:mrow><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">22</mml:mn></mml:msub></mml:mrow><mml:mo>-</mml:mo><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:mrow></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M215" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:msub><mml:mi>C</mml:mi><mml:mtext>org</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col7">CPI</oasis:entry>
         <oasis:entry colname="col8">ACL</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">[% DW]</oasis:entry>
         <oasis:entry colname="col3">(mass)</oasis:entry>
         <oasis:entry colname="col4">[<inline-formula><mml:math id="M216" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>g per gram of DW]</oasis:entry>
         <oasis:entry colname="col5">[<inline-formula><mml:math id="M217" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>g per gram of OC]</oasis:entry>
         <oasis:entry colname="col6">[‰]</oasis:entry>
         <oasis:entry colname="col7"/>
         <oasis:entry colname="col8"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">Upper reach</oasis:entry>
         <oasis:entry colname="col2">1.8 <inline-formula><mml:math id="M218" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5</oasis:entry>
         <oasis:entry colname="col3">11.8 <inline-formula><mml:math id="M219" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.0</oasis:entry>
         <oasis:entry colname="col4">7.0 <inline-formula><mml:math id="M220" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.8</oasis:entry>
         <oasis:entry colname="col5">280.2 <inline-formula><mml:math id="M221" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 165.0</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M222" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>21.87 <inline-formula><mml:math id="M223" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.84</oasis:entry>
         <oasis:entry colname="col7">8.6 <inline-formula><mml:math id="M224" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.7</oasis:entry>
         <oasis:entry colname="col8">30.4 <inline-formula><mml:math id="M225" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Floodplain</oasis:entry>
         <oasis:entry colname="col2">3.2 <inline-formula><mml:math id="M226" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.6</oasis:entry>
         <oasis:entry colname="col3">14.7 <inline-formula><mml:math id="M227" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.7</oasis:entry>
         <oasis:entry colname="col4">2.9 <inline-formula><mml:math id="M228" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.4</oasis:entry>
         <oasis:entry colname="col5">124.5 <inline-formula><mml:math id="M229" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 81.7</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M230" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>19.65 <inline-formula><mml:math id="M231" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.19</oasis:entry>
         <oasis:entry colname="col7">6.2 <inline-formula><mml:math id="M232" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.9</oasis:entry>
         <oasis:entry colname="col8">30.7 <inline-formula><mml:math id="M233" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Swamp</oasis:entry>
         <oasis:entry colname="col2">4.6 <inline-formula><mml:math id="M234" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.7</oasis:entry>
         <oasis:entry colname="col3">14.1 <inline-formula><mml:math id="M235" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.1</oasis:entry>
         <oasis:entry colname="col4">4.7 <inline-formula><mml:math id="M236" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.9</oasis:entry>
         <oasis:entry colname="col5">114.3 <inline-formula><mml:math id="M237" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 32.9</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M238" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>20.86 <inline-formula><mml:math id="M239" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.86</oasis:entry>
         <oasis:entry colname="col7">7.5 <inline-formula><mml:math id="M240" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.7</oasis:entry>
         <oasis:entry colname="col8">30.6 <inline-formula><mml:math id="M241" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Delta</oasis:entry>
         <oasis:entry colname="col2">1.5 <inline-formula><mml:math id="M242" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3</oasis:entry>
         <oasis:entry colname="col3">11.4 <inline-formula><mml:math id="M243" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.4</oasis:entry>
         <oasis:entry colname="col4">1.6 <inline-formula><mml:math id="M244" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.8</oasis:entry>
         <oasis:entry colname="col5">89.0 <inline-formula><mml:math id="M245" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 23.3</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M246" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>19.66 <inline-formula><mml:math id="M247" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.45</oasis:entry>
         <oasis:entry colname="col7">6.8 <inline-formula><mml:math id="M248" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.0</oasis:entry>
         <oasis:entry colname="col8">30.4 <inline-formula><mml:math id="M249" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.4</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Lake</oasis:entry>
         <oasis:entry colname="col2">1.6 <inline-formula><mml:math id="M250" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1</oasis:entry>
         <oasis:entry colname="col3">12.9 <inline-formula><mml:math id="M251" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.2</oasis:entry>
         <oasis:entry colname="col4">1.8 <inline-formula><mml:math id="M252" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3</oasis:entry>
         <oasis:entry colname="col5">119.5 <inline-formula><mml:math id="M253" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 20.2</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M254" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>19.36 <inline-formula><mml:math id="M255" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.73</oasis:entry>
         <oasis:entry colname="col7">5.5 <inline-formula><mml:math id="M256" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.2</oasis:entry>
         <oasis:entry colname="col8">29.8 <inline-formula><mml:math id="M257" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.1</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e3072">Displayed are the median and the median absolute deviation of analyzed parameters. For CPI and ACL, the averages and standard deviations are displayed.</p></table-wrap-foot></table-wrap>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><?xmltex \currentcnt{4}?><?xmltex \def\figurename{Figure}?><label>Figure 4</label><caption><p id="d1e3661">Box-and-whisker plots show total organic carbon content as a percent of dry weight (<bold>a</bold>), carbon-to-nitrogen ratios (<bold>b</bold>), summed concentration of long-chain <italic>n</italic>-alkanes normalized to dry weight (<bold>c</bold>), and summed concentration of long-chain <italic>n</italic>-alkanes normalized to organic carbon (<bold>d</bold>) of all surface sediments. The colors of each box refer to the assigned sub-environments of the Mkhuze Wetland System. Note that the <inline-formula><mml:math id="M258" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axis of <bold>(a)</bold> and <bold>(b)</bold> is broken.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f04.png"/>

        </fig>

</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><title>Thermal analysis of bulk organic matter</title>
      <p id="d1e3710">The HI values show a decreasing trend from the upstream (ca. 115 mg <inline-formula><mml:math id="M259" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC for upper reach and 100 mg <inline-formula><mml:math id="M260" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC for floodplain; Fig. <xref ref-type="fig" rid="Ch1.F5"/>a) to the downstream sub-environments (ca. 75 mg <inline-formula><mml:math id="M261" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC for swamp and delta; ca. 60 mg <inline-formula><mml:math id="M262" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC for lake; Fig. <xref ref-type="fig" rid="Ch1.F5"/>a). The range around the mean value is generally small (ca. 25 mg <inline-formula><mml:math id="M263" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC), except for floodplain samples which displayed a high variability, ranging between ca. 50 and 135 mg <inline-formula><mml:math id="M264" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC (Fig. <xref ref-type="fig" rid="Ch1.F5"/>a). The <inline-formula><mml:math id="M265" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula>-index values show a comparable pattern with decreasing mean values from upstream (<inline-formula><mml:math id="M266" display="inline"><mml:mrow><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.60</mml:mn></mml:mrow></mml:math></inline-formula> for upper reach and floodplain; Fig. <xref ref-type="fig" rid="Ch1.F5"/>b) to downstream sub-environments (<inline-formula><mml:math id="M267" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.60</mml:mn></mml:mrow></mml:math></inline-formula> for swamp, delta, and lake; Fig. <xref ref-type="fig" rid="Ch1.F5"/>b). The highest values were measured in floodplain samples (<inline-formula><mml:math id="M268" display="inline"><mml:mrow><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.65</mml:mn></mml:mrow></mml:math></inline-formula>, Fig. <xref ref-type="fig" rid="Ch1.F5"/>b), while swamp samples displayed the highest variance, splitting into two groups (ca. 0.55 and 0.65, Fig. <xref ref-type="fig" rid="Ch1.F5"/>b). The <inline-formula><mml:math id="M269" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula>-index values revealed an inverse pattern with low values in upstream sub-environments (ca. 0.1 for upper reach and floodplain, Fig. <xref ref-type="fig" rid="Ch1.F5"/>c), high values for the downstream sub-environments (ca. 0.3 for delta and lake, Fig. <xref ref-type="fig" rid="Ch1.F5"/>c), and swamp samples divided into two groups (ca. 0.06 and 0.22, Fig. <xref ref-type="fig" rid="Ch1.F5"/>c).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5" specific-use="star"><?xmltex \currentcnt{5}?><?xmltex \def\figurename{Figure}?><label>Figure 5</label><caption><p id="d1e3830">Displayed are the indices determined by Rock-Eval analyses. The hydrogen Index (HI, <bold>a</bold>), <inline-formula><mml:math id="M270" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index (<bold>b</bold>),
and <inline-formula><mml:math id="M271" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index (<bold>c</bold>), as introduced by <xref ref-type="bibr" rid="bib1.bibx78" id="text.91"/>, are
displayed grouped by assigned sub-environments (see Fig. <xref ref-type="fig" rid="Ch1.F1"/> and Sect. <xref ref-type="sec" rid="Ch1.S3.SS1.SSS1"/>) of the Mkhuze
Wetland System.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f05.png"/>

        </fig>

      <p id="d1e3870">In the <inline-formula><mml:math id="M272" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram (Fig. <xref ref-type="fig" rid="Ch1.F6"/>) the studied samples are projected onto the decomposition line describing the linear relationship between <inline-formula><mml:math id="M273" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> and <inline-formula><mml:math id="M274" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> when the gradual decomposition of the most labile constituents controls the OM transformation (i.e., stabilization). Lake and delta samples contain the most labile OM (<inline-formula><mml:math id="M275" display="inline"><mml:mrow><mml:mi>R</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.57</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M276" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.25</mml:mn></mml:mrow></mml:math></inline-formula>, Fig. <xref ref-type="fig" rid="Ch1.F6"/>) while upper reach and floodplain samples contain the most stable OM (<inline-formula><mml:math id="M277" display="inline"><mml:mrow><mml:mi>R</mml:mi><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.62</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M278" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.25</mml:mn></mml:mrow></mml:math></inline-formula>, Fig. <xref ref-type="fig" rid="Ch1.F6"/>) with swamp samples falling in between these extremes (Fig. <xref ref-type="fig" rid="Ch1.F6"/>). It is important to highlight that floodplain and swamp samples display high dispersion around the decomposition line in comparison with the strong correlation (<inline-formula><mml:math id="M279" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.9</mml:mn></mml:mrow></mml:math></inline-formula>) usually observed for composts, litters, and topsoils <xref ref-type="bibr" rid="bib1.bibx1 bib1.bibx78" id="paren.92"/>.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6"><?xmltex \currentcnt{6}?><?xmltex \def\figurename{Figure}?><label>Figure 6</label><caption><p id="d1e3978"><inline-formula><mml:math id="M280" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram. Symbol colors reflect the sub-environment (see Fig. <xref ref-type="fig" rid="Ch1.F1"/> and Sect. <xref ref-type="sec" rid="Ch1.S3.SS1.SSS1"/>) origin of the sedimentary organic matter: red denotes upper reach; orange denotes floodplain; green denotes swamp; yellow denotes delta; blue denotes lake. The grey-shaded area bordered by dashed grey lines refers to the linear regression describing the continuum from biological tissue to a mixture of decomposition constituents <xref ref-type="bibr" rid="bib1.bibx56" id="paren.93"><named-content content-type="pre">decomposition line;</named-content></xref>. Green circles and squares denote splitting up of swamp samples into groups of differing degradation state, while grey-bordered ellipses indicate more general splitting of the data set into groups regardless of their depositional origin.</p></caption>
          <?xmltex \igopts{width=170.716535pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f06.png"/>

        </fig>

</sec>
<sec id="Ch1.S4.SS3">
  <label>4.3</label><?xmltex \opttitle{Distribution patterns and stable carbon isotopic composition of \textit{n}-alkanes}?><title>Distribution patterns and stable carbon isotopic composition of <italic>n</italic>-alkanes</title>
      <p id="d1e4019">All surface sediment samples analyzed contained long-chain, odd-numbered <italic>n</italic>-alkanes (C<inline-formula><mml:math id="M281" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula> to C<inline-formula><mml:math id="M282" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>). The carbon preference index (CPI) has average values of 6.8 <inline-formula><mml:math id="M283" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.5 for all surface sediments, confirming that <italic>n</italic>-alkanes originated from plant waxes due to the characteristic odd-over-even dominance. The CPI of the collected plant samples was 11.4 <inline-formula><mml:math id="M284" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.4. The average chain length (ACL) for surface sediment samples was 30.2 <inline-formula><mml:math id="M285" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.5, reflecting the high proportion of longer-chain <italic>n</italic>-alkanes, and 29.6 <inline-formula><mml:math id="M286" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.9 for plant samples.</p>
<sec id="Ch1.S4.SS3.SSS1">
  <label>4.3.1</label><title>Plant samples</title>
      <p id="d1e4085">The sampled plants can be distinguished from each other based on their relative <italic>n</italic>-alkane distribution patterns and corresponding <inline-formula><mml:math id="M287" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C signatures. Aquatic plants belonging to the Nymphaeaceae family (common water lilies) show a symmetrical distribution around the two dominant <italic>n</italic>-alkanes C<inline-formula><mml:math id="M288" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">27</mml:mn></mml:msub></mml:math></inline-formula> (31.2 % <inline-formula><mml:math id="M289" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.7 %) and C<inline-formula><mml:math id="M290" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> (33.0 % <inline-formula><mml:math id="M291" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 4.8 %) (Fig. <xref ref-type="fig" rid="Ch1.F7"/>a). Similarly, <italic>P. australis</italic> (common reed), an emergent aquatic plant species, also shows high concentration of the C<inline-formula><mml:math id="M292" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">27</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane (22.1 % <inline-formula><mml:math id="M293" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.2 %), but the dominance of C<inline-formula><mml:math id="M294" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> (41.9 % <inline-formula><mml:math id="M295" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 9.9 %) determines the <italic>n</italic>-alkane distribution pattern (Fig. <xref ref-type="fig" rid="Ch1.F7"/>b). Based on their stable carbon isotope signatures, these aquatic plants are classified as C<inline-formula><mml:math id="M296" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> plants (Nymphaeaceae, <inline-formula><mml:math id="M297" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M298" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">30.60</mml:mn></mml:mrow></mml:math></inline-formula> ‰ <inline-formula><mml:math id="M299" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.61 ‰; <italic>P. australis</italic>, <inline-formula><mml:math id="M300" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M301" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">34.99</mml:mn></mml:mrow></mml:math></inline-formula> ‰ <inline-formula><mml:math id="M302" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.55 ‰).
The C<inline-formula><mml:math id="M303" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> (<inline-formula><mml:math id="M304" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M305" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">20.53</mml:mn></mml:mrow></mml:math></inline-formula> ‰) wetland sedge <italic>C. papyrus</italic> (common papyrus, Fig. <xref ref-type="fig" rid="Ch1.F7"/>c) shows a symmetrical distribution around the dominant <italic>n</italic>-alkane C<inline-formula><mml:math id="M306" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> (31.9 %) accompanied by comparatively similar contributions of the <italic>n</italic>-alkanes C<inline-formula><mml:math id="M307" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> (19.5 %) and C<inline-formula><mml:math id="M308" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> (12.8 %). It is striking that the sum of the relative concentrations of the long-chain, odd-numbered <italic>n</italic>-alkanes is just over 70 %; the remainder is accounted for by the respective even-numbered <italic>n</italic>-alkanes, of which C<inline-formula><mml:math id="M309" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">32</mml:mn></mml:msub></mml:math></inline-formula> (15.3 %) has the largest share. The distribution pattern of another Cyperaceae species, namely the C<inline-formula><mml:math id="M310" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> (<inline-formula><mml:math id="M311" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M312" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">38.87</mml:mn></mml:mrow></mml:math></inline-formula> ‰) plant <italic>C. alternifolius</italic> (umbrella papyrus, Fig. <xref ref-type="fig" rid="Ch1.F7"/>d), is characterized by predominantly the C<inline-formula><mml:math id="M313" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane (66.1 %).
Wetland grasses, such as C<inline-formula><mml:math id="M314" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> (<inline-formula><mml:math id="M315" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M316" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">18.66</mml:mn></mml:mrow></mml:math></inline-formula> ‰ <inline-formula><mml:math id="M317" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.21 ‰) plant <italic>V. cuspidata</italic> (hippo grass, Fig. <xref ref-type="fig" rid="Ch1.F7"/>e), exhibit co-dominant concentrations of the <italic>n</italic>-alkanes C<inline-formula><mml:math id="M318" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">27</mml:mn></mml:msub></mml:math></inline-formula> (27.9 % <inline-formula><mml:math id="M319" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.9 %) and C<inline-formula><mml:math id="M320" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> (26.8 % <inline-formula><mml:math id="M321" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.3 %) homologues going along with the occurrence of the very long-chain <italic>n</italic>-alkanes C<inline-formula><mml:math id="M322" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> (11.7 % <inline-formula><mml:math id="M323" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.6 %), C<inline-formula><mml:math id="M324" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> (8.9 % <inline-formula><mml:math id="M325" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.5 %), and C<inline-formula><mml:math id="M326" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula> (9.4 % <inline-formula><mml:math id="M327" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.5 %). <italic>Cynodon dactylon</italic> (bermuda grass, Fig. <xref ref-type="fig" rid="Ch1.F7"/>f), another C<inline-formula><mml:math id="M328" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> (<inline-formula><mml:math id="M329" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M330" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">22.10</mml:mn></mml:mrow></mml:math></inline-formula> ‰ <inline-formula><mml:math id="M331" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06 ‰) wetland grass, is clearly determined by the low dispersion around the dominant very long-chain <italic>n</italic>-alkane C<inline-formula><mml:math id="M332" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> dictating the appearance of the distribution with a 56.7 % <inline-formula><mml:math id="M333" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 8.8 % share (C<inline-formula><mml:math id="M334" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">23.5</mml:mn></mml:mrow></mml:math></inline-formula> % <inline-formula><mml:math id="M335" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 11.8 %, and C<inline-formula><mml:math id="M336" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">8.1</mml:mn></mml:mrow></mml:math></inline-formula> % <inline-formula><mml:math id="M337" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 6.5 %).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7" specific-use="star"><?xmltex \currentcnt{7}?><?xmltex \def\figurename{Figure}?><label>Figure 7</label><caption><p id="d1e4685">Green-colored bars show the relative
concentration of long-chain, odd-numbered <italic>n</italic>-alkanes (C<inline-formula><mml:math id="M338" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula>–C<inline-formula><mml:math id="M339" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula>) of Nymphaeaceae <bold>(a)</bold>,
<italic>Phragmites australis</italic> <bold>(b)</bold>, <italic>Cyperus papyrus</italic>
<bold>(c)</bold>, <italic>Cyperus alternifolius</italic> <bold>(d)</bold>,
<italic>Vossia cuspidata</italic> <bold>(e)</bold>, and <italic>Cynodon dactylon</italic>
<bold>(f)</bold>. Black circles represent corresponding carbon isotope values
in reference to Vienna Pee Dee Belemnite (‰ VPDB) of each
<italic>n</italic>-alkane. Error bars represent the respective standard deviation. When several representatives of one species were analyzed <bold>(a, b, e, f)</bold>, the error bars reflect natural heterogeneity, while for the others they reflect the analytical uncertainty. When the analytical errors in repeated measurements are below 0.3 ‰, the intra-laboratory long-term error (<inline-formula><mml:math id="M340" display="inline"><mml:mo lspace="0mm">±</mml:mo></mml:math></inline-formula> 0.3 ‰) is displayed instead. The same routine applies to <italic>n</italic>-alkanes if no repeated measurement was possible due to insufficient sample quantity.</p></caption>
            <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f07.png"/>

          </fig>

</sec>
<sec id="Ch1.S4.SS3.SSS2">
  <label>4.3.2</label><title>Surface sediments</title>
      <p id="d1e4775">Figure <xref ref-type="fig" rid="Ch1.F8"/> shows the relative concentrations of <italic>n</italic>-alkanes and their stable isotopic signatures for carbon and hydrogen in surface sediments within each sub-environment of the Mkhuze Wetland. For simplicity, not all individual <italic>n</italic>-alkanes are displayed, but a reduced representation is shown. For reduction, the individual <italic>n</italic>-alkanes are grouped so that only the parameters of their representatives are shown to illustrate the exemplary trends.
This grouping was made on the basis of visual criteria (trends across the wetland system) and verified by statistical means. The results of a principal component analysis (not shown) provide information about variables that contain redundant information. For further validation, the coefficients of the linear correlation between the individual variables were used. All methods show that the following grouping is justified: (i) the parameters shown for the C<inline-formula><mml:math id="M341" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane also reflect trends in the C<inline-formula><mml:math id="M342" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane (contribution <inline-formula><mml:math id="M343" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.72</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M344" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M345" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C <inline-formula><mml:math id="M346" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.91</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M347" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>); (ii) the parameters shown of the C<inline-formula><mml:math id="M348" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane also reflect the trends of the C<inline-formula><mml:math id="M349" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula>  <italic>n</italic>-alkane (contribution <inline-formula><mml:math id="M350" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.61</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M351" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M352" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C <inline-formula><mml:math id="M353" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.86</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M354" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M355" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D <inline-formula><mml:math id="M356" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.66</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M357" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>); and (iii) the presented parameter trends of the C<inline-formula><mml:math id="M358" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane are also representative of the C<inline-formula><mml:math id="M359" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane (contribution <inline-formula><mml:math id="M360" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.55</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M361" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M362" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C <inline-formula><mml:math id="M363" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.95</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M364" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>). The C<inline-formula><mml:math id="M365" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">27</mml:mn></mml:msub></mml:math></inline-formula> homologue shows a correlation with both C<inline-formula><mml:math id="M366" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula> (<inline-formula><mml:math id="M367" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C <inline-formula><mml:math id="M368" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.90</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M369" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M370" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D <inline-formula><mml:math id="M371" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.78</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M372" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>) and C<inline-formula><mml:math id="M373" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> (<inline-formula><mml:math id="M374" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C <inline-formula><mml:math id="M375" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.90</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M376" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M377" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D <inline-formula><mml:math id="M378" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.82</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M379" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>) for the stable isotope values but no stronger correlation in terms of relative contribution to any of the homologues (<inline-formula><mml:math id="M380" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.5</mml:mn></mml:mrow></mml:math></inline-formula>).
The medium-chain <italic>n</italic>-alkanes C<inline-formula><mml:math id="M381" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M382" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula> show an increasing contribution downstream (upper reach <inline-formula><mml:math id="M383" display="inline"><mml:mo>→</mml:mo></mml:math></inline-formula> floodplain <inline-formula><mml:math id="M384" display="inline"><mml:mo>→</mml:mo></mml:math></inline-formula> swamp <inline-formula><mml:math id="M385" display="inline"><mml:mo>→</mml:mo></mml:math></inline-formula> delta <inline-formula><mml:math id="M386" display="inline"><mml:mo>→</mml:mo></mml:math></inline-formula> lake), the contribution of C<inline-formula><mml:math id="M387" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula> ranging from 1.5 % <inline-formula><mml:math id="M388" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.3 % in the upper reach sub-environment to 5.4 % <inline-formula><mml:math id="M389" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.9 % in the lake sub-environment (Fig. <xref ref-type="fig" rid="Ch1.F8"/>a). The corresponding stable carbon isotope signatures show a <inline-formula><mml:math id="M390" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>/</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> mixed signal (Fig. <xref ref-type="fig" rid="Ch1.F8"/>d) with enhanced influence of C<inline-formula><mml:math id="M391" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> vegetation in the upper reach and swamp sub-environments, respectively (Fig. <xref ref-type="fig" rid="Ch1.F8"/>d). <inline-formula><mml:math id="M392" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D values show similar ranges for the upper reach to the swamp sub-environment with a slight decrease in mean values downstream and more enriched values in samples from the delta and lake sub-environment (Fig. <xref ref-type="fig" rid="Ch1.F8"/>g).
The long-chain <italic>n</italic>-alkanes C<inline-formula><mml:math id="M393" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M394" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> show similar contributions to all sub-environments (C<inline-formula><mml:math id="M395" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub><mml:mo>,</mml:mo><mml:mn mathvariant="normal">13.6</mml:mn></mml:mrow></mml:math></inline-formula> % <inline-formula><mml:math id="M396" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.1 %; C<inline-formula><mml:math id="M397" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mo>,</mml:mo><mml:mn mathvariant="normal">22.1</mml:mn></mml:mrow></mml:math></inline-formula> % <inline-formula><mml:math id="M398" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.1 %), except for a significantly stronger contribution in the upper reach samples (C<inline-formula><mml:math id="M399" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub><mml:mo>,</mml:mo><mml:mn mathvariant="normal">18.4</mml:mn></mml:mrow></mml:math></inline-formula> % <inline-formula><mml:math id="M400" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.1 %; C<inline-formula><mml:math id="M401" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub><mml:mo>,</mml:mo><mml:mn mathvariant="normal">28.8</mml:mn></mml:mrow></mml:math></inline-formula> % <inline-formula><mml:math id="M402" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.1 %; <inline-formula><mml:math id="M403" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>; Fig.<xref ref-type="fig" rid="Ch1.F8"/>b). The corresponding stable carbon isotope signatures show a stronger influence of C<inline-formula><mml:math id="M404" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> vegetation (Fig. <xref ref-type="fig" rid="Ch1.F8"/>e). Decreasing mean <inline-formula><mml:math id="M405" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D values were observed from the upper reach sub-environment (mean <inline-formula><mml:math id="M406" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D <inline-formula><mml:math id="M407" display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">140.8</mml:mn></mml:mrow></mml:math></inline-formula> ‰, Fig. <xref ref-type="fig" rid="Ch1.F8"/>h) to the swamp sub-environment (mean <inline-formula><mml:math id="M408" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D <inline-formula><mml:math id="M409" display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">153.3</mml:mn></mml:mrow></mml:math></inline-formula> ‰, Fig. <xref ref-type="fig" rid="Ch1.F8"/>h). The hydrogen isotopic composition of the long-chain <italic>n</italic>-alkanes in the downstream lake sub-environment (Fig. <xref ref-type="fig" rid="Ch1.F8"/>h) was in contrast significantly higher (mean <inline-formula><mml:math id="M410" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D <inline-formula><mml:math id="M411" display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">133.9</mml:mn></mml:mrow></mml:math></inline-formula> ‰) compared to the swamp and floodplain sub-environments (<inline-formula><mml:math id="M412" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>).
The very long-chain <italic>n</italic>-alkanes C<inline-formula><mml:math id="M413" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M414" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula> contribute on average 22.6 % <inline-formula><mml:math id="M415" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 3.8 % (C<inline-formula><mml:math id="M416" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula>) and 6.5 % <inline-formula><mml:math id="M417" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.7 % (C<inline-formula><mml:math id="M418" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>) to all sub-environments, with a maximum contribution in samples from the swamp region (C<inline-formula><mml:math id="M419" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula>, 27.6 % <inline-formula><mml:math id="M420" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 7.5 %; C<inline-formula><mml:math id="M421" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>, 8.8 % <inline-formula><mml:math id="M422" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.2 %; Fig. <xref ref-type="fig" rid="Ch1.F8"/>c). Carbon isotopic values of the very long-chain <italic>n</italic>-alkanes show a large C<inline-formula><mml:math id="M423" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> vegetation influence in the upper reach sub-environment and large variance in the floodplain sub-environment associated with a strong C<inline-formula><mml:math id="M424" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> influence that decreases slightly thereafter (Fig. <xref ref-type="fig" rid="Ch1.F8"/>f). The hydrogen isotopic composition was similar across all sub-environments, apart from the lake samples, which were characterized by elevated values (Fig. <xref ref-type="fig" rid="Ch1.F8"/>i).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8" specific-use="star"><?xmltex \currentcnt{8}?><?xmltex \def\figurename{Figure}?><label>Figure 8</label><caption><p id="d1e5737">Box-and-whisker plots show the relative
concentration in percent <bold>(a</bold>, <bold>d</bold>, <bold>g)</bold>, carbon isotope
signatures with respect to VPDB in per mil <bold>(b</bold>, <bold>e</bold>, <bold>h)</bold> and hydrogen isotope signatures with respect to VSMOW in per mil <bold>(c</bold>, <bold>f</bold>, <bold>i)</bold> of the <italic>n</italic>-alkanes C<inline-formula><mml:math id="M425" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula>, C<inline-formula><mml:math id="M426" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula>, and C<inline-formula><mml:math id="M427" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> as representatives of the groups of <italic>n</italic>-alkanes classified as
aquatic, mixed, and grassy.</p></caption>
            <?xmltex \igopts{width=284.527559pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f08.png"/>

          </fig>

</sec>
</sec>
</sec>
<sec id="Ch1.S5">
  <label>5</label><title>Discussion</title>
<sec id="Ch1.S5.SS1">
  <label>5.1</label><?xmltex \opttitle{Plants \textit{n}-alkane distribution patterns as indicators of variable hydrological conditions}?><title>Plants <italic>n</italic>-alkane distribution patterns as indicators of variable hydrological conditions</title>
      <p id="d1e5830">Differences in <italic>n</italic>-alkane distribution patterns between plant species have previously been observed in numerous studies <xref ref-type="bibr" rid="bib1.bibx29 bib1.bibx13 bib1.bibx6 bib1.bibx54" id="paren.94"/>. We are aware that the use of <italic>n</italic>-alkane distribution patterns to distinguish plant species and chemotaxonomic fingerprinting approaches is more controversial when transferring findings from one area to another, as it has been shown that variations can also occur within specific species and even between plant parts of the same species <xref ref-type="bibr" rid="bib1.bibx12" id="paren.95"/>. Because all investigated plants, however, are from the same system and, when possible, multiple plants of the same species were sampled in different sub-environments of the wetland system, we believe that influences such as variability due to different climatic growing conditions and intra-species variability are small. Although this study investigates a rather small plant sample set, the obtained data show very good agreement with the literature (as discussed in more detail in the following text). For this reason, we are confident that the assignment of specific <italic>n</italic>-alkanes as marker compounds provides realistic indicators of inputs of dominantly occurring plants when performing intra-system comparisons especially when combined with information provided by compound-specific isotope analyses.</p>
      <p id="d1e5848">Aquatic plant species such as the floating <italic>Nymphaea</italic> spp. (common water lily) and the emergent wetland sedge <italic>P. australis</italic> (common reed) are primarily found in stagnant or slow-flowing waters. These two C<inline-formula><mml:math id="M428" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> plants (Fig. <xref ref-type="fig" rid="Ch1.F7"/>a and b) show elevated concentrations of the medium-chain <italic>n</italic>-alkanes (C<inline-formula><mml:math id="M429" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">23</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M430" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">25</mml:mn></mml:msub></mml:math></inline-formula>), while all other investigated plants show no or negligible concentrations (Fig. <xref ref-type="fig" rid="Ch1.F7"/>c to f). The occurrence of the medium-chain <italic>n</italic>-alkanes, although in previous studies reported as predominant alkanes of the respective distribution patterns <xref ref-type="bibr" rid="bib1.bibx5 bib1.bibx29 bib1.bibx53" id="paren.96"/>, therefore seems to be explicitly indicative of aquatic plant types.
The riparian zone along the Mkhuze River is dominated by typical woody plants of riparian forests, such as <italic>A. xanthophloea</italic> (fever tree) and <italic>F. sycomorus</italic> (sycamore fig) <xref ref-type="bibr" rid="bib1.bibx61" id="paren.97"/>. While no representative of these species was sampled in this study, woody plants, such as trees, are generally well studied <xref ref-type="bibr" rid="bib1.bibx91" id="paren.98"/>. Tropical C<inline-formula><mml:math id="M431" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> trees are typically characterized by high C<inline-formula><mml:math id="M432" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M433" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane contributions (in sum <inline-formula><mml:math id="M434" display="inline"><mml:mrow><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">75</mml:mn></mml:mrow></mml:math></inline-formula> %), while the adjacent homologues show concentration mainly below 5 %. Especially the C<inline-formula><mml:math id="M435" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane was recently described as “a responsive sensor” of tropical tree vegetation <xref ref-type="bibr" rid="bib1.bibx98" id="paren.99"/>, which further corroborates its earlier observed tree bias <xref ref-type="bibr" rid="bib1.bibx30" id="paren.100"/>. However, we pursue identifying alkane homologues which are present in certain plant types and absent or only very low concentrated in others so that they can serve as marker compounds for system-specific vegetation types. For this reason and given the high contributions of this alkane to nearly all displayed distribution patterns, we decided to regard the C<inline-formula><mml:math id="M436" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M437" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane as more of an integrated signal which possibly originates from a diverse range of plants.</p>
      <p id="d1e5992">The wetland sedges <italic>C. papyrus</italic> (Papyrus; C<inline-formula><mml:math id="M438" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>) and <italic>C. alternifolius</italic> (Umbrella papyrus; C<inline-formula><mml:math id="M439" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>) (Fig. <xref ref-type="fig" rid="Ch1.F7"/>c and d) predominantly produce C<inline-formula><mml:math id="M440" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkanes, a finding consistent with the limited data available <xref ref-type="bibr" rid="bib1.bibx16" id="paren.101"/>. Their natural occurrence is restricted to permanently flooded soils, whereas C<inline-formula><mml:math id="M441" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> wetland grasses such as <italic>V. cuspidata</italic> (hippopotamus grass) or <italic>Cynodon dactylon</italic> (Bermuda grass) (Fig. <xref ref-type="fig" rid="Ch1.F7"/>e and f) are mostly tolerant of intermittent soil flooding and other disturbances <?xmltex \hack{\mbox\bgroup}?><xref ref-type="bibr" rid="bib1.bibx40" id="paren.102"/><?xmltex \hack{\egroup}?>, so they generally occur widely. Like many (sub)tropical grasses these plant types are characterized by the presence of the very long-chain <italic>n</italic>-alkanes (C<inline-formula><mml:math id="M442" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">33</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M443" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">35</mml:mn></mml:msub></mml:math></inline-formula>) <xref ref-type="bibr" rid="bib1.bibx71 bib1.bibx92" id="paren.103"/>, which cannot be found in relevant concentrations in the other investigated plants (Fig. <xref ref-type="fig" rid="Ch1.F7"/>).</p>
</sec>
<sec id="Ch1.S5.SS2">
  <label>5.2</label><title>Spatial comparison of organic matter characteristics in surface sediments</title>
      <p id="d1e6095">Clear differences between the individual sub-environments of the Mkhuze Wetland System become evident by comparing the organic matter characteristics with respect to stability, degree of degradation, primary contributing vegetation, and its hydrological growth conditions. That these differences sometimes appear small in absolute values is attributable to the system itself. The discussed sub-environments (see Sect. <xref ref-type="sec" rid="Ch1.S3.SS1.SSS1"/>) cannot be separated from each other by sharp boundaries, but rather the transitions are shown to be gradual in their ecological manifestations. That the characteristics of the OM differ despite this gradual transformation underscores the importance of the individual environments to the system.</p>
<sec id="Ch1.S5.SS2.SSS1">
  <label>5.2.1</label><title>Upper reach of the Mkhuze River</title>
      <p id="d1e6107">Bulk organic matter in surface sediments of the upper reach is generally low in concentration (see Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>a) and shows geochemical and thermal characteristics of degraded OM (HI <inline-formula><mml:math id="M444" display="inline"><mml:mo>≅</mml:mo></mml:math></inline-formula> 120 mg per gram of TOC, <inline-formula><mml:math id="M445" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M446" display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">11.8</mml:mn></mml:mrow></mml:math></inline-formula>  <inline-formula><mml:math id="M447" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>  1.0; Figs. <xref ref-type="fig" rid="Ch1.F5"/>a and <xref ref-type="fig" rid="Ch1.F4"/>b), which can be related to an advanced decomposition of thermally labile constituents (<inline-formula><mml:math id="M448" display="inline"><mml:mrow><mml:mi>R</mml:mi><mml:mo>≅</mml:mo><mml:mn mathvariant="normal">0.63</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M449" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.15</mml:mn></mml:mrow></mml:math></inline-formula>; linear distribution within the limits of the decomposition line in the <inline-formula><mml:math id="M450" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram; Fig. <xref ref-type="fig" rid="Ch1.F6"/>).
The concentration of <italic>n</italic>-alkanes from plant waxes per dry weight and organic carbon is highest in the surface sediments of the upper reach (Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>c–d), suggesting relative enrichment due to OM degradation. The relative contribution of long-chain <italic>n</italic>-alkanes C<inline-formula><mml:math id="M451" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> and C<inline-formula><mml:math id="M452" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F8"/>d) is also highest while carrying the lowest carbon isotopic signature (Fig. <?xmltex \hack{\mbox\bgroup}?><xref ref-type="fig" rid="Ch1.F8"/>e)<?xmltex \hack{\egroup}?> of all sub-environments. Recently, it was shown that especially the C<inline-formula><mml:math id="M453" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> <italic>n</italic>-alkane might serve as a responsive sensor for tropical tree vegetation <?xmltex \hack{\mbox\bgroup}?><xref ref-type="bibr" rid="bib1.bibx98" id="paren.104"/><?xmltex \hack{\egroup}?>. Regarding the upper reaches and despite the C<inline-formula><mml:math id="M454" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> cluster serving as integrated signal from all plant contributions, the strong deviation of the relative contribution and carbon isotopic composition of this cluster in comparison with all other sub-environments suggests that sedimentary OM of the upper reach is indeed dominated by inputs of woody plant sources. OM in the surface sediments of the upper reach therefore reflects allochthonous contributions from the hinterland, since the Mkhuze River is primarily lined with riparian forests <xref ref-type="bibr" rid="bib1.bibx61" id="paren.105"/>. These trees do not tolerate flooding or water-saturated soil conditions, so they are found on the elevated channel levees. This interpretation of the hinterland as an origin is further supported by the stable hydrogen isotopes of the respective <italic>n</italic>-alkanes, particularly evident in C<inline-formula><mml:math id="M455" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula> (Fig. <xref ref-type="fig" rid="Ch1.F8"/>f). The relatively enriched <inline-formula><mml:math id="M456" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D values suggest that the plants producing them were exposed to relatively dry conditions during their growth phase. These dry conditions are met to a large extent in the hinterland, considering that the precipitation gradient across the Mkhuze Wetland System is nearly halved from 1000 mm yr<inline-formula><mml:math id="M457" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in the east near the coast to 600 mm yr<inline-formula><mml:math id="M458" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> at the Lebombo Mountains (<xref ref-type="bibr" rid="bib1.bibx57" id="altparen.106"/>; Fig. <xref ref-type="fig" rid="Ch1.F2"/>).</p>
</sec>
<sec id="Ch1.S5.SS2.SSS2">
  <label>5.2.2</label><title>Floodplain</title>
      <p id="d1e6320">Bulk organic matter in surface sediments of the floodplain is characterized by high variability in both quantity (TOC, Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>a) and quality (HI, <inline-formula><mml:math id="M459" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> and <inline-formula><mml:math id="M460" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> indices, Fig. <xref ref-type="fig" rid="Ch1.F5"/>a–c). It splits into three groups: the first one corresponds to samples poor in OM (TOC <inline-formula><mml:math id="M461" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">1.5</mml:mn></mml:mrow></mml:math></inline-formula> %) and in hydrocarbon compounds (HI <inline-formula><mml:math id="M462" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">80</mml:mn></mml:mrow></mml:math></inline-formula> mg <inline-formula><mml:math id="M463" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC). A second group corresponds to samples rich in OM (TOC <inline-formula><mml:math id="M464" display="inline"><mml:mrow><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:math></inline-formula> %) and hydrocarbon compounds (HI <inline-formula><mml:math id="M465" display="inline"><mml:mrow><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mn mathvariant="normal">150</mml:mn></mml:mrow></mml:math></inline-formula> mg <inline-formula><mml:math id="M466" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC). The third group presents an intermediate situation (TOC <inline-formula><mml:math id="M467" display="inline"><mml:mo>≈</mml:mo></mml:math></inline-formula> 2 %–3 %, HI <inline-formula><mml:math id="M468" display="inline"><mml:mo>≈</mml:mo></mml:math></inline-formula> 100 mg <inline-formula><mml:math id="M469" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC). An explanation could consider that this gradual evolution corresponds to a more or less advanced degradation of the sedimentary OM. However, the <inline-formula><mml:math id="M470" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index does not support this interpretation, since the samples with the lowest HI present the least advanced degree of decomposition of thermally labile compounds (<inline-formula><mml:math id="M471" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.1</mml:mn></mml:mrow></mml:math></inline-formula>) and conversely. In addition, floodplain samples show a wide dispersion in the <inline-formula><mml:math id="M472" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram (Fig. <xref ref-type="fig" rid="Ch1.F6"/>), which excludes a gradual decomposition. By analogy with previous work on soils, such nonlinear signatures would rather be associated with OM mixtures of varying quality and origin, which is consistent with such a heterogeneous depositional environment.</p>
      <p id="d1e6458">Mixing of OM is further corroborated by the plant-wax concentration per dry weight and organic carbon (Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>c–d) showing great variances and therefore that <italic>n</italic>-alkanes are partly relatively enriched during not only degradation of OM but also inputs of fresh organic material, which is in line with elevated <inline-formula><mml:math id="M473" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula> ratios (Fig. <xref ref-type="fig" rid="Ch1.F4"/>b). High variability is also evident in the relative contributions of the <italic>n</italic>-alkanes (Fig. <xref ref-type="fig" rid="Ch1.F8"/>a, d, g) and the corresponding isotopic signatures (Fig. <xref ref-type="fig" rid="Ch1.F8"/>b, e, h), suggesting a mixture of OM of different origin. The floodplain of the Mkhuze Wetland System is characterized by a mosaic of different smaller wetland types, ranging from the locally distinct river channel to seasonally flooded areas to permanent (open) water bodies. The ecologically complex and variable diversity is reflected in all the parameters. However, it is noteworthy that, despite this predominant scatter, the strongest input of C<inline-formula><mml:math id="M474" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> vegetation is clearly observed in floodplain sedimentary organic matter (Fig. <xref ref-type="fig" rid="Ch1.F8"/>b, e, h). This cannot be explained solely by the occurrence of C<inline-formula><mml:math id="M475" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> grasses such as <italic>Cynodon dactylon</italic> or <italic>Echinochloa pyramidalis</italic>, which are recognized as important floodplain vegetation communities <xref ref-type="bibr" rid="bib1.bibx61" id="paren.107"/>, since the “grassy” <italic>n</italic>-alkane input is not significantly higher than in the downstream swamp (Fig. <xref ref-type="fig" rid="Ch1.F8"/>g). In addition, <xref ref-type="bibr" rid="bib1.bibx61" id="text.108"/> describes the floodplain being increasingly used for growing crops, such as the C<inline-formula><mml:math id="M476" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> crops sugarcane or corn (Fig. <xref ref-type="fig" rid="Ch1.F3"/>), which could explain the particularly strong C<inline-formula><mml:math id="M477" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> signal.</p>
</sec>
<sec id="Ch1.S5.SS2.SSS3">
  <label>5.2.3</label><title>Swamp</title>
      <p id="d1e6557">The bulk organic matter in surface sediments of the swamp sub-environment is similarly characterized by high variability in both quantity (TOC, Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>a) and quality (HI, <inline-formula><mml:math id="M478" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> and <inline-formula><mml:math id="M479" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> indices, Fig. <xref ref-type="fig" rid="Ch1.F5"/>a–c). As for floodplain samples, swamp samples show high dispersion depending on their OM and hydrocarbon content with both contents decreasing downstream, suggesting a more or less advanced degradation of the sedimentary OM. Similarly to the floodplain sub-environment, the <inline-formula><mml:math id="M480" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index opposes this assumption, as the samples with the lowest HI (HI <inline-formula><mml:math id="M481" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">75</mml:mn></mml:mrow></mml:math></inline-formula>) correspond to the least advanced degree of decomposition (<inline-formula><mml:math id="M482" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.2</mml:mn></mml:mrow></mml:math></inline-formula>), pointing towards a mixture of OM related to overprinting of fluvially introduced OM by in situ-produced OM. The <inline-formula><mml:math id="M483" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mo>/</mml:mo><mml:mi>R</mml:mi></mml:mrow></mml:math></inline-formula> diagram, while samples are globally aligned with the decomposition line, also reveals two distinct clusters (Fig. <?xmltex \hack{\mbox\bgroup}?><xref ref-type="fig" rid="Ch1.F6"/><?xmltex \hack{\egroup}?> green circles and squares) showing a degraded and much less degraded signature, respectively. These results indicate that the swamp sub-environment contains a wide range of situations, such as those similar to upstream (upper reach, floodplain) and downstream (delta, lake) sub-environments, and therefore reflects a transitional sub-environment. Furthermore, the organic matter is characterized by comparatively high <inline-formula><mml:math id="M484" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula> ratios, i.e., corroborating the addition of in situ-produced organic matter to the samples. This is also seen in the summed concentration of <italic>n</italic>-alkanes normalized to dry weight (Fig. <xref ref-type="fig" rid="Ch1.F4"/>c) being very high, while those normalized to organic carbon (Fig. <xref ref-type="fig" rid="Ch1.F4"/>d) are rather low, which is attributed to fresh organic matter inputs.</p>
      <p id="d1e6646">A similar pattern to that for the bulk organic matter can also be observed in the plant-wax data. While the <italic>n</italic>-alkane distribution closely resembles that of the floodplain (Fig. <xref ref-type="fig" rid="Ch1.F8"/>a, d, g), the corresponding carbon isotope signatures (Fig. <xref ref-type="fig" rid="Ch1.F8"/>b, e, h) show a slightly lower influence of C<inline-formula><mml:math id="M485" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> vegetation and rather a mixed <inline-formula><mml:math id="M486" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>/</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> signal with slightly increasing C<inline-formula><mml:math id="M487" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> vegetation influence downstream. This can be explained by the increased input of the locally dominant vegetation into the sedimentary organic matter (overprinting), although to a moderate extent. The Mkhuze Swamps are dominated by the C<inline-formula><mml:math id="M488" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> wetland sedge <italic>P. australis</italic> (Fig. <xref ref-type="fig" rid="Ch1.F7"/>b) occurring along the eastern margin and large stands of the C<inline-formula><mml:math id="M489" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> wetland grass <italic>Cynodon dactylon</italic> (Fig. <xref ref-type="fig" rid="Ch1.F7"/>f) at the western side of the river channel. Limited overprinting of fluvially transported OM by local vegetation is further supported by the slightly lighter hydrogen isotopic composition of the respective <italic>n</italic>-alkanes (Fig. <xref ref-type="fig" rid="Ch1.F8"/>c, f, i) indicating only slightly wetter growth conditions in the swamp area compared to the floodplain although water availability is much more persistent within the swamp area.</p>
</sec>
<sec id="Ch1.S5.SS2.SSS4">
  <label>5.2.4</label><title>Delta and lake</title>
      <p id="d1e6736">The organic matter of the lake and delta samples shows striking differences when compared with that of the upstream sub-environments of the Mkhuze Wetland System. The bulk organic matter in surface sediments shows a homogeneous signature with the lowest contents in OM (TOC <inline-formula><mml:math id="M490" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">1.6</mml:mn></mml:mrow></mml:math></inline-formula> %, Table <xref ref-type="table" rid="Ch1.T1"/> and Fig. <xref ref-type="fig" rid="Ch1.F4"/>a) and hydrocarbon compounds (HI <inline-formula><mml:math id="M491" display="inline"><mml:mrow><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mn mathvariant="normal">80</mml:mn></mml:mrow></mml:math></inline-formula> mg <inline-formula><mml:math id="M492" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">HC</mml:mi></mml:mrow></mml:math></inline-formula> per gram of TOC, Fig. <xref ref-type="fig" rid="Ch1.F5"/>a) of all sub-environments and a high degree of preservation of thermally labile fractions (<inline-formula><mml:math id="M493" display="inline"><mml:mrow><mml:mi>I</mml:mi><mml:mi mathvariant="italic">&gt;</mml:mi><mml:mn mathvariant="normal">0.3</mml:mn></mml:mrow></mml:math></inline-formula>, partly in the upper limit of the decomposition line). These results differ drastically from the OM results of the upstream sub-environments, but they do not reflect aquatic autochthonous contributions (as indicated by the low HI). Although the sources of this OM are probably terrestrial, it is not detrital (allochthonous) OM, reworked from the catchment area, but rather a proximal (para-autochthonous) contribution.</p>
      <p id="d1e6787">In contrast to bulk OM, the relative contribution of all marker <italic>n</italic>-alkane clusters (aquatic, mixed, and grassy) (Fig. <xref ref-type="fig" rid="Ch1.F8"/>a, d, g) and their corresponding <inline-formula><mml:math id="M494" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>/</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> signatures (Fig. <xref ref-type="fig" rid="Ch1.F8"/>b, e, h) are not significantly different from the upstream sub-environments. This implies that the sources of plant waxes regarding vegetation type are similar or possibly even the same as upstream. However, considering that the scatter of the compound-specific carbon isotopic composition correlates with the diversity of contributing vegetation types <?xmltex \hack{\mbox\bgroup}?><xref ref-type="bibr" rid="bib1.bibx55" id="paren.109"/><?xmltex \hack{\egroup}?>, the narrow spread of stable and bulk carbon isotope signatures (Fig. <xref ref-type="fig" rid="Ch1.F8"/>b, e, h and Table <xref ref-type="table" rid="Ch1.T1"/>) suggests that a more restricted range of plant types contributes to lake surface sediments. The associated hydrogen isotopic signatures (Fig. <xref ref-type="fig" rid="Ch1.F8"/>c, f, i) indicate that the contributing plants, although very similar to the upstream sub-environments, experienced completely different hydrological conditions during growth. The <italic>n</italic>-alkanes in the lake surface sediments have a higher median <inline-formula><mml:math id="M495" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D compared to that of the upstream swamp by about 10 <inline-formula><mml:math id="M496" display="inline"><mml:mi mathvariant="normal">‰</mml:mi></mml:math></inline-formula> (C<inline-formula><mml:math id="M497" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">31</mml:mn></mml:msub></mml:math></inline-formula>) to 20.0 <inline-formula><mml:math id="M498" display="inline"><mml:mi mathvariant="normal">‰</mml:mi></mml:math></inline-formula> (C<inline-formula><mml:math id="M499" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">29</mml:mn></mml:msub></mml:math></inline-formula>). There are several scenarios which could explain these significantly higher <inline-formula><mml:math id="M500" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D values. Considering that the upstream swamp area and the sampled lake transect are located in the same longitudinal range, the variation in sedimentary <inline-formula><mml:math id="M501" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D is therefore reflecting neither variation in precipitation amount nor isotopic depletion due to inland movement of water vapor, like in the case of the upper reach sub-environment. Given the geomorphological and climatic characteristics of Lake St Lucia (shallow average depth, large surface area, strong wind regime, and high evaporation rates and salinity), the higher hydrogen isotope signatures of the sedimentary <italic>n</italic>-alkanes in the lake probably resulted from a dominant contribution of vegetation, which uses the lake's water as a dominant water source. Considering that not only the hydrogen isotopic composition of sedimentary plant-wax-derived <italic>n</italic>-alkanes but also the previously discussed bulk parameters show striking differences compared to the swamp area more or less excludes the concept of a contribution of a sole unknown “end-member” which alters all mentioned variables except relative <italic>n</italic>-alkane concentration and their carbon isotopic composition although only minimally contributing. All in all, the most reasonable explanation is that the majority of the organic matter in the lake area is not derived from the upstream sub-environments, although this might be unexpected.</p>
</sec>
</sec>
<sec id="Ch1.S5.SS3">
  <label>5.3</label><title>Transport of sedimentary organic matter in the Mkhuze Wetland System</title>
      <p id="d1e6903">Characterization of organic matter in surface soils and sediments in terms of its stability, degree of decomposition, and source vegetation, as well as the hydrological conditions in the sub-environments of the Mkhuze Wetland System, allows us to evaluate transport pathways. Plant-wax lipids are hydrophobic and associated with the mineral component of sediments <xref ref-type="bibr" rid="bib1.bibx33 bib1.bibx51 bib1.bibx97" id="paren.110"/>. Thus, the transport and identification of sources and sinks are not exclusive to the organic component of the sediment.
In the Mkhuze Wetland System, sedimentary organic matter derived from the Mkhuze River catchment (hinterland) is primarily deposited on the floodplain but also reaches the Mkhuze Swamps. Under present conditions, Lake St Lucia does not receive significant quantities of sedimentary material from the hinterland or material exported from the Mkhuze Swamps. Cores retrieved from Lake St Lucia <xref ref-type="bibr" rid="bib1.bibx9" id="paren.111"/> and the Mkhuze River bayhead delta <xref ref-type="bibr" rid="bib1.bibx42" id="paren.112"/> indicate that sedimentary infilling commenced 6000–7000 years ago when the main oceanic inlets at Lake St Lucia sealed in response to rising sea levels during the Holocene transgression. This deposited sediment gave rise to the establishment of the current Mkhuze Swamps which currently act as an effective trap, preventing the rapid siltation of the lake. An exception might be large disruptive events (severe droughts or strong floods) which occur occasionally and could induce erosion of the swamp or bypassing of its filter capacity.
The high concentration of plant waxes in the upper reach of the Mkhuze River is due to low-flow conditions during the sampling campaign. During the spring season, the river typically has low or even no flow <xref ref-type="bibr" rid="bib1.bibx58" id="paren.113"/>, resulting in the deposition of suspended sediment in the riverbed. The upper reach samples collected in this study thus likely reflect the “undiluted” hinterland signal (highly degraded, stable, C<inline-formula><mml:math id="M502" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula>, most likely of woody origin). During periods of high flow, transported fluvial OM is deposited along the river channel and on the floodplain by bank overtopping <xref ref-type="bibr" rid="bib1.bibx61 bib1.bibx25" id="paren.114"/>. The even greater stability of the organic matter in the floodplain illustrates this depositional process (Fig. <xref ref-type="fig" rid="Ch1.F5"/>b). Proportions of the organic matter found in the Mkhuze Swamps are characteristically similar to that of the floodplain, so we assume that some suspended material is transported into and deposited in this sub-environment. This is clearly shown in the <inline-formula><mml:math id="M503" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index vs. <inline-formula><mml:math id="M504" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index diagram (Fig. <xref ref-type="fig" rid="Ch1.F6"/>), which shows several clusters of samples: (i) high <inline-formula><mml:math id="M505" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index, low <inline-formula><mml:math id="M506" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index (upper reach, floodplain, swamp subset); (ii) low <inline-formula><mml:math id="M507" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index, medium <inline-formula><mml:math id="M508" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index (swamp subset); and (iii) low <inline-formula><mml:math id="M509" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index, high <inline-formula><mml:math id="M510" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index (lake and delta samples).
Surface sedimentary OM from the delta and, in particular, the lake is significantly different from the upstream sub-environments. As discussed in the previous section, not only does Lake St Lucia experience a significantly lower input of sedimentary organic matter and plant waxes, but also the deposited material does not originate from the upstream sub-environments through which the Mkhuze River flows but most likely from the shoreline around the lake.</p>
      <p id="d1e6992">Analyzed signals from the lake area are thus local in origin and reflect locally occurring eco(hydro)logical conditions. Characteristics of transported hinterland signals predominate only in the upstream areas (upper reach, floodplain, swamp), although in the floodplain and the Mkhuze Swamps slight overprinting by locally introduced signals can be observed. Based on these findings, we suggest that the Mkhuze Swamps ultimately capture material transported by the Mkhuze River and consequently the integrated signals encompassing the river catchment, at least under current climatic and environmental conditions.</p>
</sec>
<sec id="Ch1.S5.SS4">
  <label>5.4</label><title>Local ecological implications</title>
      <p id="d1e7003">The identification of the Mkhuze Swamps as the ultimate sink for suspended OM from the Mkhuze River confirms previous studies that the Mkhuze Wetland System, specifically the floodplain and swamp, acts as an efficient filter upstream of Lake St Lucia <xref ref-type="bibr" rid="bib1.bibx85 bib1.bibx81" id="paren.115"/>. The current active filtering and trapping function of high sediment loads, including organic sedimentary organic load from the Mkhuze River, may prevent the otherwise rapid siltation of Lake St Lucia. OM in the surface sediments of Lake St Lucia originates primarily from lakeshore vegetation, as indicated by the lake transect data shown in comparison with upstream areas of the system. However, some studies <xref ref-type="bibr" rid="bib1.bibx85" id="paren.116"/> assume that the Mkhuze Swamps, in their function as freshwater reservoirs (“sponges”) <xref ref-type="bibr" rid="bib1.bibx2" id="paren.117"/>, are also responsible for input of OM, serving as a potential energy source in Lake St Lucia. Our data on particulate organic matter contradict this assumption, showing that sedimentary particulate OM is presently not transported from the hinterland nor exported directly from the swamp.
In contrast, OM export from wetlands occurs primarily through the export of dissolved organic matter <xref ref-type="bibr" rid="bib1.bibx14" id="paren.118"><named-content content-type="pre">DOM;</named-content></xref>, which accounts for about 90 % of total OM <xref ref-type="bibr" rid="bib1.bibx70" id="paren.119"/>. In saline waters, like Lake St Lucia, DOM is likely to flocculate <xref ref-type="bibr" rid="bib1.bibx4" id="paren.120"/>. Assuming that OM is exported in dissolved form from the Mkhuze Swamps, it should thus be detectable in the lake transect surface samples, but this was not observed in this study. In part, this could be due to the fact that a significant proportion of DOC may be removed by sorption onto precipitating oxides when sediments contain substantial amounts of aluminum and iron metal oxides <xref ref-type="bibr" rid="bib1.bibx59" id="paren.121"/>, as is the case in upstream sub-environments. With the employed methods we cannot confirm either any particulate OC or DOC export from the Mkhuze Wetland System into Lake St Lucia.
The present study is the first examining sedimentary OM transport within the Mkhuze Wetland System, revealing that OM is indeed transported even to the Mkhuze Swamps and is not just deposited near the river channel and on the floodplain. Three processes might play a role for transport of material into the swamps: (i) the ongoing eastward progression of the floodplain <xref ref-type="bibr" rid="bib1.bibx58" id="paren.122"/>, (ii) transport during severe flood events caused by cyclones and cutoff lows, or (iii) channelization having an impact on the transport efficiency. The transport path of the Mkhuze River has been dramatically shortened by channelization (see Sect. <xref ref-type="sec" rid="Ch1.S3.SS1.SSS3"/>). As a result, most of the Mkhuze River water now flows through the Tshanetshe–Demazane Canal System <xref ref-type="bibr" rid="bib1.bibx81 bib1.bibx61 bib1.bibx7 bib1.bibx24" id="paren.123"/>, which may have altered sediment transport. A shift in the area of deposition of material transported by the Mkhuze River is likely to affect the local vegetation distribution, i.e., causing a shift in the ecological zones by altered substrate conditions. In general, however, the Mkhuze Wetland System overall appears to exhibit high resilience against natural and/or anthropogenically induced changes. The severe drought of 2016, which led to the drying of large parts of Lake St Lucia, does not seem to have had any lasting impact on the filtering function of the swamps. Likewise, the establishment of the canal system also does not appear to have caused lasting damage to the filtering function of the Mkhuze Swamps.</p>

      <?xmltex \floatpos{h!}?><fig id="Ch1.F9" specific-use="star"><?xmltex \currentcnt{9}?><?xmltex \def\figurename{Figure}?><label>Figure 9</label><caption><p id="d1e7040">The figure shows a schematic summary of the characteristics and transport pathways of organic material in a terminal or flow-through wetland system under low-flow conditions. The vegetation types shown (trees, wetland sedges, grasses, and aquatic species) indicate the prominently occurring vegetation in each sub-environment of the Mkhuze Wetland System. Arrows indicate OM input and deposition, with thickness of arrows corresponding to OM quantity assumptions and colors corresponding to OM quality characteristics (dark brown: more degraded; light brown: less degraded, spatially different origin).</p></caption>
          <?xmltex \igopts{width=469.470472pt}?><graphic xlink:href="https://bg.copernicus.org/articles/19/2881/2022/bg-19-2881-2022-f09.png"/>

        </fig>

</sec>
<sec id="Ch1.S5.SS5">
  <label>5.5</label><title>Fate of sedimentary organic matter in wetlands</title>
      <p id="d1e7058">In  comparison with humid-region (tropical and temperate) wetlands, the Mkhuze Wetland System exhibits distinctive characteristics that reflect the low ratio between precipitation and potential evapotranspiration characterizing the region (Fig. 2). High evaporative demand and transmission losses from the river to the surrounding floodplain result in marked declines in both channel width and channel depth downstream <xref ref-type="bibr" rid="bib1.bibx43" id="paren.124"/>. Downstream decreases in discharge and stream power result in a gradual decline in the ability of the Mkhuze River to transport particulate material, ultimately terminating in the Mkhuze Swamps. Although typically unusual, such downstream changes appear to be distinctive features of wetlands found in sub-humid and semi-arid regions of the world <xref ref-type="bibr" rid="bib1.bibx89" id="paren.125"/> and are likely an important reason why the Mkhuze Wetland System acts as such an efficient trap for organic material.
Most large tropical and temperate river systems are associated with wetlands <xref ref-type="bibr" rid="bib1.bibx95 bib1.bibx93" id="paren.126"/> along their river courses. For example, studies conducted on the Cuvette Congolaise <xref ref-type="bibr" rid="bib1.bibx73" id="paren.127"/>, a large wetland system traversed by the Congo River, indicate that fluvially transported particulate OM signals from upstream sources are seasonally overprinted by storage and release of particulates in and from the wetlands <xref ref-type="bibr" rid="bib1.bibx34 bib1.bibx35" id="paren.128"/>. Depending on variable climatic conditions throughout the year, the Cuvette Congolaise wetlands may thus show a similar trapping function of transported material to the Mkhuze Wetland System under relatively dry conditions while showing increased export from material at higher water flows <xref ref-type="bibr" rid="bib1.bibx35" id="paren.129"/>. Wetlands may thus switch from a trapping function to export of carbon depending on hydrological conditions and seasonal climatic changes.
These differential trapping and export functions of wetlands need to be considered when reconstructing climatic changes based on sedimentary archives recovered from terminal lakes and offshore archives. Depending on the activity and efficiency of wetlands, material from more upstream areas will be effectively masked by wetlands depending on their hydrologic state and can even be overprinted be wetland export of OM or OM input from downstream areas. Such a process has been suggested for the transport of OM in the Amazon River system, where Andean material is effectively overprinted by lowland sources from rainforests, floodplains, and wetlands <xref ref-type="bibr" rid="bib1.bibx67 bib1.bibx11" id="paren.130"/>. In such cases, reconstructing environmental changes in the integrated watershed using offshore archives may thus not be possible. Wetland systems with an active trapping function effectively change the transported OM, so signals detected in offshore archives instead reflect specific sections of the river catchment. Other sediment-related proxies may also be affected by wetland trapping, so such geomorphological settings could have a much stronger influence than is often assumed. Combining environmental analyses with specific markers released from wetlands, on the other hand, allows an assessment of the hydrologic changes that lead to inefficient OM trapping and degradation of wetlands <xref ref-type="bibr" rid="bib1.bibx76" id="paren.131"><named-content content-type="pre">e.g., </named-content></xref>.
In addition, carbon sequestration and the ability of wetlands to act as carbon sinks are considered to play an important role in the global carbon budget. There is concern that global warming may alter the hydrological balance of wetlands, releasing significant amounts of carbon to the atmosphere through direct oxidation processes or to adjacent water bodies through erosion of wetland soils, as has been observed for the Cuvette Congolaise and elsewhere <xref ref-type="bibr" rid="bib1.bibx35" id="paren.132"/>. In certain cases, extreme weather events, which are expected to become more frequent as the global climate changes, have also been shown to promote the release of DOC from wetlands <xref ref-type="bibr" rid="bib1.bibx72" id="paren.133"/>. It is likely that particulate material would also be exported by excessive flooding, as is similarly observed by increased flushing of terrestrial carbon into river systems <xref ref-type="bibr" rid="bib1.bibx10" id="paren.134"/>. Thus, the trapping function of wetlands, overridden by overloading, would just as likely contribute to increased carbon dioxide emissions to the atmosphere through turnover of exported OM in adjacent waters.</p>
</sec>
</sec>
<sec id="Ch1.S6" sec-type="conclusions">
  <label>6</label><title>Conclusions</title>
      <p id="d1e7106">We present a spatial assessment of TOC concentrations, OM composition (<inline-formula><mml:math id="M511" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C, <inline-formula><mml:math id="M512" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">N</mml:mi></mml:mrow></mml:math></inline-formula>, HI, <inline-formula><mml:math id="M513" display="inline"><mml:mi>R</mml:mi></mml:math></inline-formula> index, <inline-formula><mml:math id="M514" display="inline"><mml:mi>I</mml:mi></mml:math></inline-formula> index), <italic>n</italic>-alkane distributions, and their respective compound-specific stable carbon (<inline-formula><mml:math id="M515" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C<inline-formula><mml:math id="M516" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi>n</mml:mi><mml:mtext>-alkane</mml:mtext></mml:mrow></mml:msub></mml:math></inline-formula>) and hydrogen (<inline-formula><mml:math id="M517" display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D<inline-formula><mml:math id="M518" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi>n</mml:mi><mml:mtext>-alkane</mml:mtext></mml:mrow></mml:msub></mml:math></inline-formula>) isotope compositions along an approx. 130 km long transect of the Mkhuze River and plant-wax data from locally dominant plant species to constrain the origin and transport pathways of OM through and within the sub-environments of the Mkhuze Wetland System, South Africa. Our results indicate that degraded OM originating from the hinterland is deposited primarily on the floodplain of the Mkhuze River and partially in the downstream swamp. The Mkhuze Swamps currently efficiently trap OM under low-flow conditions, so they neither release hinterland material nor export swamp-derived OM to Lake St Lucia (Fig. <xref ref-type="fig" rid="Ch1.F9"/>).</p>
      <p id="d1e7194">The surface sediments in the upper reach show allochthonous inputs from the Mkhuze River basin. OM concentrations are low and show a degraded signature associated with a C<inline-formula><mml:math id="M519" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:math></inline-formula> woody source vegetation which experienced relatively dry growing conditions. Sedimentary OM in the floodplain and swamp exhibits high variability in both source signatures and degradation status, thus reflecting environmental diversity. A mixture of degraded OM from the hinterland and fresh OM of local origin characterizes samples from the floodplain area. In addition, the most pronounced C<inline-formula><mml:math id="M520" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> signatures are encountered and attributed to agricultural use of the floodplain. OM from surface samples in the Mkhuze Swamps also shows a degraded signature but reflects increasing inputs of local wetland sedges and wetland grasses. In contrast, OM from Lake St Lucia shows completely different characteristics, such as much lower concentrations and much less degradation due to proximal terrestrial inputs rather than reworked catchment-derived or aquatic contributions. Plant-wax data confirm these findings, pointing to lake shoreline vegetation as the main source.</p>
      <p id="d1e7215">This study shows that traversed or terminal wetlands under certain conditions, such as low flow – in this case a result of climatic factors, i.e., with evaporation exceeding precipitation – can capture OM so efficiently that transport from upstream areas does not occur and downstream OM originates almost exclusively from the immediate vicinity. We emphasize that such wetlands, as geomorphological features within river systems, can impact environmental studies, which assume watershed-integrated signals based on terminal sediments. In addition, disturbances, e.g., by extreme weather events, which are assumed to become more frequent under global climate change, are likely to affect the trapping function of wetlands and thus increase export of previously stored OM, leading to an increase in carbon emissions through turnover of exported OM in adjacent water bodies.</p>
</sec>

      
      </body>
    <back><notes notes-type="dataavailability"><title>Data availability</title>

      <p id="d1e7222">The research data are available at PANGAEA: <ext-link xlink:href="https://doi.org/10.1594/PANGAEA.935586" ext-link-type="DOI">10.1594/PANGAEA.935586</ext-link> <xref ref-type="bibr" rid="bib1.bibx32" id="paren.135"/></p>
  </notes><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e7233">MZ, ES, AH, and MSH conceptualized the project; MZ and ES directed the project and acquired financial support for the project leading to this publication; DS characterized the samples with Rock-Eval analysis and interpreted related results; JG performed sample preparation and measurements, processed the data, and drafted the manuscript; MSH and JG designed figures; JG took the lead in writing the manuscript. All authors provided critical feedback and helped shape it.</p>
  </notes><?xmltex \hack{\newpage}?><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e7240">The contact author has declared that neither they nor their co-authors have any competing interests.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d1e7246">Publisher’s note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e7252">We would sincerely like to thank Letitia Pillay, Archibold Buah-Kwofie, and Lucky for their expertise, support, and energetic assistance in obtaining the material studied. Additionally, we particularly thank Lucky for his assistance in communicating with the local landowners. We thank Marcus Elvert and Hendrik Reuter for their contributions to previous versions of the paper. This study would also not have been possible without the help of technicians Ralph Kreutz and Jenny Wendt of MARUM – Center for Marine Environmental Sciences. We thank them for their support in chemical analyses and thank student assistant Abdullah Saeed Khan for assisting in bulk organic matter analyses. We thank Marion Bamford and Frank Neumann for their support and help with identifying the plant samples. We are grateful to Daniel Pillot and Herman Ravelojaona (IFPEN) for their technical and scientific support in Rock-Eval<sup>®</sup> analysis, a trademark registered by IFP Energies Nouvelles. The anonymous reviewers as well as the associate editor Sebastian Naeher are thanked very much for their critical comments and constructive advice that helped to improve this publication. Moreover, we thank the GeoB Core Repository at MARUM and PANGAEA for archiving the sediments and data used in this work. We thank Ezemvelo KZN Wildlife and iSimangaliso Wetland Park Authority for permitting us to work at Lake St Lucia. Samples were collected under the registered project, “A multi-proxy investigation into past and present environmental change at Lake St Lucia”.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e7260">This work was financially supported by the German Federal
Ministry of Education and Research (BMBF, Bonn, Germany) under the
project “Tracing Human and Climate impacts in South Africa” (TRACES),
project number 03F0798A.<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> The article processing charges for this open-access<?xmltex \notforhtml{\newline}?> publication were covered by the University of Bremen.</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e7272">This paper was edited by Sebastian Naeher and reviewed by two anonymous referees.</p>
  </notes><ref-list>
    <title>References</title>

      <ref id="bib1.bibx1"><?xmltex \def\ref@label{{Albrecht et~al.(2015)Albrecht, Sebag, and Verrecchia}}?><label>Albrecht et al.(2015)Albrecht, Sebag, and Verrecchia</label><?label Albrecht2015?><mixed-citation>Albrecht, R., Sebag, D., and Verrecchia, E.: Organic matter decomposition:
bridging the gap between Rock–Eval pyrolysis and chemical characterization
(CPMAS13C NMR), Biogeochemistry, 122, 101–111,
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