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  <front>
    <journal-meta><journal-id journal-id-type="publisher">HESS</journal-id><journal-title-group>
    <journal-title>Hydrology and Earth System Sciences</journal-title>
    <abbrev-journal-title abbrev-type="publisher">HESS</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Hydrol. Earth Syst. Sci.</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1607-7938</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/hess-24-3361-2020</article-id><title-group><article-title>Pacific climate reflected in Waipuna Cave <?xmltex \hack{\break}?> drip water hydrochemistry</article-title><alt-title>Pacific climate reflected in Waipuna Cave drip water hydrochemistry</alt-title>
      </title-group><?xmltex \runningtitle{Pacific climate reflected in Waipuna Cave drip water hydrochemistry}?><?xmltex \runningauthor{C.~Nava-Fernandez et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Nava-Fernandez</surname><given-names>Cinthya</given-names></name>
          <email>cinthya.navafernandez@rub.de</email>
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Hartland</surname><given-names>Adam</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Gázquez</surname><given-names>Fernando</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff9">
          <name><surname>Kwiecien</surname><given-names>Ola</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4 aff5">
          <name><surname>Marwan</surname><given-names>Norbert</given-names></name>
          
        <ext-link>https://orcid.org/0000-0003-1437-7039</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff6 aff2">
          <name><surname>Fox</surname><given-names>Bethany</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff7">
          <name><surname>Hellstrom</surname><given-names>John</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-9427-3525</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Pearson</surname><given-names>Andrew</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-2170-6606</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Ward</surname><given-names>Brittany</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>French</surname><given-names>Amanda</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff8">
          <name><surname>Hodell</surname><given-names>David A.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Immenhauser</surname><given-names>Adrian</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff9">
          <name><surname>Breitenbach</surname><given-names>Sebastian F. M.</given-names></name>
          
        <ext-link>https://orcid.org/0000-0001-9615-2065</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Department for Sediment- and Isotope Geology, Institute for Geology, Mineralogy and Geophysics, <?xmltex \hack{\break}?> Ruhr-Universität Bochum, Universitätsstr. 150, 44801 Bochum, Germany</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Environmental Research Institute, School of Science, Faculty of
Science and Engineering, <?xmltex \hack{\break}?> University of Waikato, Hamilton, Waikato, New Zealand</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Department of Biology and Geology, Universidad de Almería, Almería, 04120, Spain</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>Potsdam Institute for Climate Impact Research (PIK), Member of the
Leibniz Association, Potsdam, Germany</institution>
        </aff>
        <aff id="aff5"><label>5</label><institution>Institute of Geosciences, University of Potsdam, Potsdam, Germany</institution>
        </aff>
        <aff id="aff6"><label>6</label><institution>Department of Biological and Geographical Sciences, School of Applied Sciences, <?xmltex \hack{\break}?> University of Huddersfield, Queensgate, Huddersfield, UK</institution>
        </aff>
        <aff id="aff7"><label>7</label><institution>School of Earth Sciences, The University of Melbourne, Melbourne, Australia</institution>
        </aff>
        <aff id="aff8"><label>8</label><institution>Godwin Laboratory for Palaeoclimate Research, Department of Earth
Sciences, <?xmltex \hack{\break}?> University of Cambridge, Downing Street, Cambridge, CB2 3EQ, UK</institution>
        </aff>
        <aff id="aff9"><label>a</label><institution>now at: Department of Geography and Environmental Sciences, <?xmltex \hack{\break}?> Northumbria University, Newcastle upon Tyne, NE1 8ST, UK</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Cinthya Nava-Fernandez (cinthya.navafernandez@rub.de)</corresp></author-notes><pub-date><day>1</day><month>July</month><year>2020</year></pub-date>
      
      <volume>24</volume>
      <issue>6</issue>
      <fpage>3361</fpage><lpage>3380</lpage>
      <history>
        <date date-type="received"><day>2</day><month>December</month><year>2019</year></date>
           <date date-type="rev-request"><day>27</day><month>January</month><year>2020</year></date>
           <date date-type="rev-recd"><day>8</day><month>May</month><year>2020</year></date>
           <date date-type="accepted"><day>29</day><month>May</month><year>2020</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2020 Cinthya Nava-Fernandez et al.</copyright-statement>
        <copyright-year>2020</copyright-year>
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020.html">This article is available from https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020.html</self-uri><self-uri xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020.pdf">The full text article is available as a PDF file from https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020.pdf</self-uri>
      <abstract><title>Abstract</title>
    <p id="d1e258">Cave microclimate and geochemical monitoring is vitally important for
correct interpretations of proxy time series from speleothems with regard to past climatic and environmental dynamics. We present results of a
comprehensive cave-monitoring programme in Waipuna Cave in the North Island
of New Zealand, a region that is strongly influenced by the Southern
Westerlies and the El Niño–Southern Oscillation (ENSO). This study aims to characterise the response of the Waipuna Cave hydrological system to atmospheric circulation dynamics in the southwestern Pacific region in order to assure the quality of ongoing palaeo-environmental reconstructions from this cave.</p>
    <p id="d1e261">Drip water from 10 drip sites was collected at roughly monthly intervals for
a period of ca. 3 years for isotopic (<inline-formula><mml:math id="M1" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M2" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>, d-excess parameter, <inline-formula><mml:math id="M3" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M4" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) and elemental (<inline-formula><mml:math id="M5" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M6" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula>) analysis. The monitoring included spot measurements of drip rates and cave air <inline-formula><mml:math id="M7" 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> concentration. Cave air temperature and drip rates were also continuously recorded by automatic loggers. These datasets were compared to surface air temperature, rainfall, and potential evaporation from nearby meteorological stations to test the degree of signal transfer and expression of surface environmental conditions in Waipuna Cave hydrochemistry.</p>
    <p id="d1e351">Based on the drip response dynamics to rainfall and other characteristics, we
identified three types of discharge associated with hydrological routing in
Waipuna Cave: (i) type 1 – diffuse flow, (ii) type 2 – fracture flow, and (iii) type 3 – combined flow. Drip water isotopes do not reflect seasonal
variability but show higher values during severe drought. Drip water <inline-formula><mml:math id="M8" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values are characterised by small variability and reflect the mean isotopic signature of precipitation, testifying to rapid and thorough homogenisation in the epikarst. <inline-formula><mml:math id="M9" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M10" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios in drip waters are predominantly controlled by prior calcite precipitation (PCP). Prior calcite precipitation is strongest during austral summer (December–February), reflecting drier conditions and a lack of<?pagebreak page3362?> effective infiltration, and is weakest during the wet austral winter (July–September). The <inline-formula><mml:math id="M11" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratio is particularly sensitive to ENSO conditions due to the interplay of congruent or incongruent host rock dissolution, which manifests itself in lower <inline-formula><mml:math id="M12" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> in above-average warmer and wetter (La Niña-like) conditions. Our
microclimatic observations at Waipuna Cave provide a valuable baseline for the
rigorous interpretation of speleothem proxy records aiming at reconstructing
the past expression of Pacific climate modes.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e424">The southwestern fringe of the Pacific Ocean between 30 and 40<inline-formula><mml:math id="M13" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> S marks the transition zone between the tropical Pacific and the sub-tropical Southern Ocean. This region's position near the boundary of two markedly different climates makes the southwestern Pacific a key site to capture the signatures of the coupled atmosphere–ocean climate sub-systems of the El Niño–Southern Oscillation (ENSO) and the Southern Westerlies (Basher, 1998; Shulmeister et al., 2004). The midlatitude Westerlies are a dominant feature in Southern Hemisphere general circulation. The prevailing wind flow from west to east over Aotearoa/New Zealand is present throughout the year but shows maximum intensity in winter (Sturman and Tapper, 2014). The westerly circulation has a significant impact on mean rainfall in New Zealand, with strong wind circulation bringing more rainfall to the western parts of the islands (Griffiths, 2006). The effects of both of these circulation features are well expressed in seasonal to multi-annual climate variability in New Zealand (Mullan, 1996). New Zealand's climate is strongly modulated by both ENSO and the Southern Westerlies, and its agricultural economy reacts sensitively to inter-annual fluctuations in weather patterns caused by their dynamics (Basher, 1998).</p>
      <p id="d1e436">During El Niño events, New Zealand is susceptible to increases in the
frequency and intensity of westerly and southwesterly winds, accompanied by
decreased rainfall in the North Island (Ummenhofer and England, 2007). In contrast, La Niña events are accompanied by stronger northeasterly winds and increased rainfall in the North Island (Griffiths, 2006; Ummenhofer and England, 2007). The link between ENSO events and climate on the western coast of the North Island of New Zealand is reflected in the correlation between precipitation and the Niño 3.4 and SOI (Southern Oscillation Index) indices (Fig. S1 in the Supplement). Rainfall in this area is negatively correlated with the Niño 3.4 index for the months June to November (austral winter), indicating that during El Niño events New Plymouth receives below average rainfall. The SOI index also shows a fairly strong correlation with austral-winter rainfall (July to November), with above-normal precipitation on the western coast during times of positive SOI values, indicative of La Niña (Fig. S1).</p>
      <p id="d1e439"><?xmltex \hack{\newpage}?>The environmental and economic impacts of strong ENSO events for New Zealand
are considerable. For example, the severe drought triggered by the strong El Niño event of 1997–1998 caused economic losses of ca. NZD 1 billion
(Basher, 1998). The projected effects of ENSO on New Zealand's hydroclimate
are based on observations of El Niño and La Niña dynamics recorded
over the instrumental period. However, such observations cover only a
comparatively short time span (beginning in the early 1800s). The study of the
long-term natural variability of New Zealand's hydroclimate (and emergent
teleconnection patterns) is a priority both because of the effects of ENSO
variability on local economic conditions and because records from this
region are sparse but vital for improving the robustness of model
projections of future ENSO conditions. Since the nature of ENSO over the
last few millennia remains poorly understood, ENSO-sensitive study sites
that provide long, robustly datable proxy reconstructions are urgently
needed. Prior to building robust palaeo-climate (ENSO) reconstructions (e.g. by using speleothems), field sites that are highly susceptible to
ENSO-related environmental changes must be identified through monitoring
campaigns.</p>
      <p id="d1e443">Speleothems (secondary cave carbonates) offer precise chronological control
and a wide range of environmentally sensitive proxies, including growth
rate, carbon, and oxygen isotopes (<inline-formula><mml:math id="M14" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M15" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>);
major and trace elements; and increasingly, non-traditional isotope systems
such as <inline-formula><mml:math id="M16" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">44</mml:mn></mml:msup><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> (Henderson, 2006; Fairchild and Baker, 2012,  7–10; Owen et al., 2016; Magiera et al., 2020) or <inline-formula><mml:math id="M17" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">26</mml:mn></mml:msup><mml:mi mathvariant="normal">Mg</mml:mi></mml:mrow></mml:math></inline-formula> (Immenhauser et al., 2010; Riechelmann et al., 2012).</p>
      <p id="d1e499">Over the last 2 decades, speleothems have provided invaluable
reconstructions of past rainfall, changes in vegetation, and coupled
atmosphere–ocean dynamics (Dorale et al., 1998; Asmerom et al., 2010; Myers
et al., 2015; Chen et al., 2016; Griffiths et al., 2016; Lechleitner et al.,
2017; Kaushal et al., 2018). Speleothems provide reliable continental
palaeo-climate records because they allow for modern calibrations linking
palaeo-data from stalagmites with meteorological and direct in-cave
monitoring, thus making it possible to trace climatic signals from the
surface to the speleothem at timescales from seasonal (Frappier et al.,
2002) to orbital (Wang et al., 2001, 2008; Meckler et al., 2012; Cheng et al., 2016). Apart from established methods, ongoing investigations are exploring the use of triple oxygen isotopes (i.e. <inline-formula><mml:math id="M18" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>; see Sect. 3.4 for definition) in carbonate and fluid inclusions in speleothems as a proxy for changes in atmospheric humidity (Affolter et al., 2015; Sha et al., 2020). In rainfall – and presumably in cave drip water – <inline-formula><mml:math id="M19" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> mostly reflects the relative humidity during the formation of water vapour at the moisture source (i.e. ocean surface), with temperature having a minor effect (Uechi and Uemura, 2019).</p>
      <p id="d1e532">The monitoring of modern cave environments, encompassing ventilation, hydrology,
and hydrochemistry, is critical for reliable interpretations of
palaeo-environmental<?pagebreak page3363?> proxies preserved in speleothems because numerous
studies have shown imperfect replication between coeval stalagmites, as well
as differences in drip water composition (McDermott, 2004; Fairchild et al.,
2006a; Breitenbach et al., 2015). Some of the key parameters affecting a
speleothem's fidelity as an environmental archive include cave air and water
temperature, drip discharge dynamics, and cave air <inline-formula><mml:math id="M20" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, as well as drip water chemistry (Fairchild and Baker, 2012, p. 110; Tremaine et al., 2016). Analysis of the latter allows a distinction to be made between the processes involved in the transfer of the external environmental signals
(e.g. precipitation history, temperature, or soil dynamics) and the
processes inherent to the epikarst and cave (e.g. degree of water–rock
interaction, seepage water <inline-formula><mml:math id="M21" 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> degassing, cave air <inline-formula><mml:math id="M22" 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> dynamics, and prior carbonate precipitation; Oster et al., 2012; Fairchild and Baker, 2012, pp. 24–27).</p>
      <p id="d1e570">The characterisation of infiltration pathways is an essential prerequisite
for delineating the processes that can modulate drip water chemistry, i.e. the degree of water–rock interaction taking place in the epikarst and the
climate signal transferred by the drip water to the speleothems. The climatic
signal transferred to speleothems can vary even between speleothems from the
same chamber, which emphasises the need for detailed monitoring. As every
stalagmite records the conditions that occur in the epikarst and which signals
transferred by the feeding drip water, an in-depth understanding of the
forcing mechanisms is vital to understand the differences between
non-replicating records.</p>
      <p id="d1e573">The physical proprieties of the karst zone define the different levels of
porosity (Ford and Williams, 2007). Primary porosity is a matrix of
inter-granular pore space; secondary porosity is associated with joints and
fractures; and tertiary porosity is associated with solution-enhanced conduits. Seepage
water experiences one or a combination of these different porosity types,
which determine hydrological pathways (Fairchild and Baker, 2012, p. 114).
Conceptual models of cave drip water hydrology have traditionally sought to
delineate these different types of flow routing on the basis of peak
discharge and discharge variability. Smart and Friederich (1987), later
modified by Baker et al. (1997), and more recently, Jex et al. (2012), Markowska
et al. (2015), and Mahmud et al. (2018) proposed new classification systems
based on long-term drip discharge time series, statistical tests, and
clustering models. These site-specific classification systems argue that
drip discharge characterisation enables a better understanding of the
controls on stalagmite growth and of climate proxies such as stable isotopes
and trace metals.</p>
      <p id="d1e576">Flow routing to speleothem drip points is the first-order control on
drip water hydrochemistry, with particular relevance for trace elements and
other proxies of prior calcite precipitation (PCP; Fairchild et al., 2000;
Wassenburg et al., 2012). PCP serves as a proxy system for moisture
availability (Magiera et al., 2020), as it controls the distribution of
trace elements in the infiltrating water during the precipitation of carbonate
depending on their partition coefficient prior to their arrival at a stalagmite.
During the dry season, when the epikarst is less water-filled, PCP can
occur, resulting in an increase in <inline-formula><mml:math id="M23" display="inline"><mml:mrow><mml:mi>X</mml:mi><mml:mo>/</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:mrow></mml:math></inline-formula> ratios in solution (and subsequently the speleothem), while during the wet season, when the epikarst is refilled, PCP is suppressed and drip water <inline-formula><mml:math id="M24" display="inline"><mml:mrow><mml:mi>X</mml:mi><mml:mo>/</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:mrow></mml:math></inline-formula> ratios are lowered (Fairchild and Treble, 2009). Common PCP proxy systems include the group II alkaline earth metals (Mg, Sr, and Ba) and stable Ca isotopes (<inline-formula><mml:math id="M25" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">44</mml:mn></mml:msup><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula>) (Magiera et al., 2020; Owen et al., 2016). Calcium isotopes show particular potential for future quantitative PCP reconstructions. However, linking PCP to rainfall amount requires careful site-specific monitoring and calibration (Li et al., 2018).</p>
      <p id="d1e618">Cave-monitoring studies in tropical and southwestern Pacific regions have
documented strong ENSO signals in Australia (Tadros et al., 2016), Borneo
(Moerman et al., 2014), and on Niue Island in the central Pacific (Tremaine
et al., 2016). In New Zealand, however, the number of comparable monitoring
studies is still limited. Williams and Fowler (2002) investigated the
relationship between the oxygen isotope composition of rainfall and
drip water in Aranui Cave (Waitomo region, North Island). They found that
neither the seasonal variability nor the ENSO-related variability detected
in <inline-formula><mml:math id="M26" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values of rainfall was transferred to the cave
drip waters. In the case of Aranui Cave, this seems to result from
the homogenisation of the water isotope signal on its path through the soil and
epikarst (Williams and Fowler, 2002). These results highlight the importance
of understanding local settings and indicate a need for revisiting other New
Zealand cave systems in order to test the relationship between external
environmental signals and those inherent to the epikarst and cave system.</p>
      <p id="d1e635">We hypothesise that the hydrochemistry of Waipuna Cave is sensitive to
changes in precipitation patterns and thus to seasonal variations and
dynamics related to ENSO and the Southern Westerlies, due to its
geographical position and geometry. Our study aims to test this hypothesis
through a 3-year cave-monitoring study, including measurements of cave
ventilation, drip water hydrochemistry, and local temperature patterns. Our
study has three consecutive objectives: (i) characterising the drip water
chemistry, including major and trace elements (<inline-formula><mml:math id="M27" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M28" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula>) and isotope geochemistry (<inline-formula><mml:math id="M29" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M30" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M31" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>, d-excess parameter, and <inline-formula><mml:math id="M32" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>);
(ii) identifying the mechanisms controlling drip water chemistry; and (iii) understanding the relationship between drip water chemistry and variations in precipitation, with special reference to seasonal and inter-annual (ENSO) climate conditions.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><?xmltex \currentcnt{1}?><label>Figure 1</label><caption><p id="d1e716"><bold>(a)</bold> Geographical location of Waipuna Cave and its climatic settings during La Niña conditions in summer 2018, with the direction of the Westerlies. Source data: OSTIA. SST: sea surface temperature. <bold>(b)</bold> Pancake limestone outcrop landscape above Waipuna Cave. <bold>(c)</bold> Cross section through the entrance and first stretch of Waipuna Cave. <bold>(d)</bold> 3D model of the “Organ Loft” chamber photo taken by John Hellstrom using structure-from-motion (SfM) mapping.</p></caption>
        <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f01.png"/>

      </fig>

</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Study area</title>
<sec id="Ch1.S2.SSx1" specific-use="unnumbered">
  <title>Geographical and climatological setting</title>
      <?pagebreak page3364?><p id="d1e749">Waipuna Cave is located in the Waitomo district, North Island, New Zealand
(38<inline-formula><mml:math id="M33" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>18<inline-formula><mml:math id="M34" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>41.3<inline-formula><mml:math id="M35" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> S, 175<inline-formula><mml:math id="M36" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>1<inline-formula><mml:math id="M37" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>14.3<inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> E; 395 m above sea
level), ca. 27 km from the western coast (Fig. 1a). The Waipuna Cave is a ca. 3.5 km long river cave developed in the clay-rich, stylobedded Oligocene pancake limestone (Nelson, 1973, Fig. 1b). The estimated bedrock overburden
is ca. 20–30 m. The main passage is accessed via a ca. 25 m deep
doline. An underground stream flowing through the cave connects a number of
larger chambers (Fig. 1c and d). The winding and narrow passage that connects
the main chambers limits cave air flow, and the cave atmosphere is
relatively isolated from the surface conditions (Fig. 1c). The surface
morphology around Waipuna Cave is characterised by a craggy-karst landscape
with frequent large dolines (Fig. 1b).</p>
      <p id="d1e813">The soil zone is generally <inline-formula><mml:math id="M39" display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> m thick Typic Orthic Allophanic (LO) developed on extensive and exceptionally well drained North Island
rhyolitic volcanic ash deposits (Hewitt, 2010). The vegetation cover is a
patchwork of lush podocarp–hardwood forest with a dense undergrowth of
shrubs, ferns, and tree ferns. This is surrounded by grassland pasture used
for grazing cattle. Based on data from Te Kuiti High School, a
meteorological station in the Waitomo district, the average conditions
during the period from 1950 to 2000 CE include annual rainfall of 1539 mm.
Summer and winter monthly precipitation means vary between 95 and 150 mm,
respectively, with the highest values in austral winter (July) and lowest values
during austral summer (February). The mean annual temperature is
13.4 <inline-formula><mml:math id="M40" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, ranging from an average of 18.5 <inline-formula><mml:math id="M41" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in summer to
8 <inline-formula><mml:math id="M42" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in winter.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Methods</title>
<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>External environmental monitoring</title>
      <p id="d1e869">Several meteorological datasets were used to constrain the relationship
between surface and in-cave environmental conditions. A HOBO temperature
logger (ONSET, Bourne, Massachusetts, USA) with a precision of  <inline-formula><mml:math id="M43" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.2</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M44" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C housed in a purpose-built meteorological station was deployed a few hundred metres from the cave entrance and recorded air
temperature at half-hourly intervals between June 2017 and May 2018, from
which daily means were calculated. The same station recorded daily rainfall
over the periods April to September 2016 and May 2017 to May 2018.
Rainfall was recorded with a precision of 0.1 mm using a combination of
Campbell Scientific (established in September 2016) and HOBO tipping-bucket
rain gauges (established May 2017). Due to technical difficulties, it was
not feasible to collect rainfall data over the entire monitoring period. To
complement the local meteorological dataset, daily rainfall, and potential
evapotranspiration (PET; based on the Priestley–Taylor equation) data were
obtained from the NIWA (National Institute of Water and Atmospheric Research) National Database (<uri>https://cliflo.niwa.co.nz/</uri>, last access: 26 June 2020) using proximal stations at Otorohanga Glenbrook and Te Kuiti Ews, 22 and 13 km from Waipuna Cave, respectively.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><?xmltex \currentcnt{2}?><label>Figure 2</label><caption><p id="d1e896"><bold>(a)</bold> Flowstone formation in the Organ Loft chamber (Photograph courtesy of Inken Heidke). <bold>(b)</bold> Drip sites at the flowstone curtain. <bold>(c)</bold> Stalactite cluster where drip site WP-3 is located, hanging from the ceiling 6 m high in an inclined plane.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f02.png"/>

        </fig>

<?xmltex \hack{\newpage}?>
</sec>
<?pagebreak page3365?><sec id="Ch1.S3.SS2">
  <label>3.2</label><title>Cave environment monitoring</title>
      <p id="d1e923">Waipuna Cave was visited at ca. monthly intervals for a period of almost 3 years from April 2016 to February 2019 (32 visits in total). Discrete cave
air <inline-formula><mml:math id="M45" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> measurements were conducted during each visit in the sampling chamber using a Vaisala CARBOCAP Carbon Dioxide Probe GMP343 with an MI70 indicator with a precision of <inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula> % of the reading. These measurements were always done before all team members entered the cave chamber to avoid
contamination. Water temperature, pH, and electrical conductivity were
manually measured on the drip waters using LAQUAtwin pH and conductivity
probes (HORIBA Scientific, Japan) calibrated prior to each sampling event.
Air temperature in the Organ Loft was recorded every 30 min throughout
the monitoring period using an automatic HOBO logger.</p>
</sec>
<sec id="Ch1.S3.SS3">
  <label>3.3</label><title>Cave water collection and drip rates</title>
      <p id="d1e957">A total of 10 drip sites, along with the cave stream, were sampled for water isotopes
and elemental concentrations. Seven of the drip sites (WP 1-1, WP 1-2, WP 1-3, WP 1-4, WP 1A, WP 1B, and WP FB) feed a flowstone (Fig. 2a and b). Three further drip sites (WP-2, WP-3, and WP-4) are located a few metres apart
below active stalactites (Fig. 2c) on an elevated section within the same
chamber and higher in the ceiling than the first seven drip sites.
Additional water samples from the cave stream were also collected (one per
visit). Drip water samples for stable isotope analysis (<inline-formula><mml:math id="M47" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>,
<inline-formula><mml:math id="M48" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M49" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>) were collected and stored in sterile 2 or 10 mL polypropylene bottles, filled with no head space and sealed using laboratory film. Water samples for trace element analysis were collected in 15 mL polypropylene (Falcon) tubes, previously demonstrated to have low metal blanks (Hartland et al., 2015). These samples were acidified with 2 % <inline-formula><mml:math id="M50" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HNO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (using in-house, double Teflon-distilled acid) and
refrigerated until analysis.</p>
      <p id="d1e1007">Drip rates at the monitored sites were determined using two independent
methods. First, spot measurements were performed at all drip sites. The
number of drips per minute was counted during each visit using a stopwatch
and counting at least 10 drips. Second, continuous measurements were carried
out at four drip sites, WP 1-1, WP 1-2, WP 1-3, and WP-2, using acoustic
Driptych Stalagmate drip loggers (<uri>http://www.driptych.com/</uri>, last access: 26 June 2020).</p>
</sec>
<sec id="Ch1.S3.SS4">
  <label>3.4</label><title>Oxygen and hydrogen isotopes of water</title>
      <?pagebreak page3366?><p id="d1e1021">The oxygen and hydrogen isotope composition (<inline-formula><mml:math id="M51" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M52" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M53" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>) of drip water and stream water was measured using cavity ring-down spectroscopy (CRDS; Steig et al., 2014). Drip water samples collected between August 2016 and April 2017 were analysed for <inline-formula><mml:math id="M54" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M55" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> using a Picarro L1102-i water isotope analyser at the Godwin Laboratory for Paleoclimate Research, University of Cambridge, UK. Samples collected between June 2017 and February 2018 were analysed for <inline-formula><mml:math id="M56" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M57" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M58" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> using a Picarro L2140-i at the School of Environmental Sciences of the University of St Andrews, UK. Samples collected from March 2018 to February 2019 were measured for <inline-formula><mml:math id="M59" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M60" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M61" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> on a Picarro L2140-i at the Department of Biology and Geology at the Universidad de Almería, Spain. This instrument permits the measurement of the triple oxygen and hydrogen isotope composition of liquid water with no sample pretreatment. The CRDS devices were interfaced with an A0211 high-precision vaporiser.</p>
      <p id="d1e1156">The results were normalised to the VSMOW (Vienna Standard Mean Ocean Water)
scale by analysing internal standards before and after a set of measurements
of 10 to 12 samples. Three internal water standards (JRW, BOTTY, and SPIT) were calibrated against VSMOW and SLAP (Standard Light Antarctic
Precipitation) using <inline-formula><mml:math id="M62" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values of 0.0 ‰ and <inline-formula><mml:math id="M63" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">29.69865</mml:mn></mml:mrow></mml:math></inline-formula> ‰, respectively, and <inline-formula><mml:math id="M64" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values of 0.0 ‰ and <inline-formula><mml:math id="M65" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">55.5</mml:mn></mml:mrow></mml:math></inline-formula> ‰, respectively (Schoenemann et al., 2013). This standardisation considers <inline-formula><mml:math id="M66" display="inline"><mml:mrow><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:math></inline-formula> for both international standards. <inline-formula><mml:math id="M67" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> was calibrated against VSMOW, GISP (Greenland Ice Sheet Precipitation), and SLAP. All isotopic deviations are reported in parts per thousand (‰) relative to VSMOW. <inline-formula><mml:math id="M68" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values are given in per meg units (0.001 ‰), where <inline-formula><mml:math id="M69" display="inline"><mml:mrow><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow><mml:mo>=</mml:mo><mml:mi>ln⁡</mml:mi><mml:mo>(</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1000</mml:mn><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.528</mml:mn><mml:mo>⋅</mml:mo><mml:mi>ln⁡</mml:mi><mml:mo>(</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1000</mml:mn><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> (Barkan and Luz, 2005). The <inline-formula><mml:math id="M70" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> expresses a small <inline-formula><mml:math id="M71" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> deviation (normally a few per meg units) of a water sample with respect to the global meteoric water line (GMWL) for triple oxygen isotopes, for which the slope is 0.528 (Luz and Barkan, 2010). The d-excess parameter describes the deviation for <inline-formula><mml:math id="M72" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M73" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> of a given sample with respect to the GMWL (<inline-formula><mml:math id="M74" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">8</mml:mn><mml:mo>⋅</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:mrow></mml:math></inline-formula>; Craig, 1961).</p>
      <p id="d1e1397">The long-term precision (1<inline-formula><mml:math id="M75" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) of oxygen and hydrogen isotope analyses
was evaluated by measuring an internal standard (BOTTY) every five to six samples.
The long-term precision of the Picarro L1102-i was <inline-formula><mml:math id="M76" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.08</mml:mn></mml:mrow></mml:math></inline-formula> ‰ for <inline-formula><mml:math id="M77" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M78" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.7</mml:mn></mml:mrow></mml:math></inline-formula> ‰ for <inline-formula><mml:math id="M79" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> (<inline-formula><mml:math id="M80" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">33</mml:mn></mml:mrow></mml:math></inline-formula>), while for the Picarro L2140-i it was <inline-formula><mml:math id="M81" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.03</mml:mn></mml:mrow></mml:math></inline-formula> ‰, <inline-formula><mml:math id="M82" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula> ‰, and <inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.4</mml:mn></mml:mrow></mml:math></inline-formula> ‰ for <inline-formula><mml:math id="M84" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M85" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M86" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>, respectively (<inline-formula><mml:math id="M87" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">43</mml:mn></mml:mrow></mml:math></inline-formula>). The
long-term precision of the d-excess parameter (<inline-formula><mml:math id="M88" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">8</mml:mn><mml:mo>⋅</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:mrow></mml:math></inline-formula>) was <inline-formula><mml:math id="M89" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.7</mml:mn></mml:mrow></mml:math></inline-formula>‰ for the Picarro L1102-i and <inline-formula><mml:math id="M90" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.3</mml:mn></mml:mrow></mml:math></inline-formula> ‰ for the Picarro L2140-i. The long-term
precision for <inline-formula><mml:math id="M91" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> was <inline-formula><mml:math id="M92" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">8</mml:mn></mml:mrow></mml:math></inline-formula> per meg. The calibrated
value of BOTTY was indistinguishable within analytical errors when using the
three different instruments, suggesting results are comparable.</p>
</sec>
<sec id="Ch1.S3.SS5">
  <label>3.5</label><title>Major and trace elements in drip water</title>
      <p id="d1e1622">Elemental and major cation concentrations in cave stream, drip water, and rainwater
were measured on two generations of instruments at the University of
Waikato. Samples collected between August 2016 and October 2017 were
analysed using a PerkinElmer ELAN quadrupole ICP-MS (inductively coupled plasma mass spectrometer), and samples collected
between November 2017 and February 2019 were analysed with an Agilent 8900
triple quadrupole ICP-MS at the Waikato Environmental Geochemistry
Laboratory. The precision of both instruments is similar, and all relative
standard deviations (RSDs) were <inline-formula><mml:math id="M93" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:math></inline-formula> %. The ICP-MS was optimised to
maximum sensitivity daily, ensuring oxides and double-charged species were
less than 2 %. External calibration standards were prepared using an
IV71-A multi-element standard from 0.1 to 500 ppb for trace elements, and
single-element standards were used to prepare calibration standards for
major elements Ca, Fe, Si, P, S, K, and Na. An internal standard containing Sc,
Ge, Te, Ir, and Rh was used for all samples. Check standards were analysed
every 20 samples and re-calibration was performed every 100 samples. Blank
samples were analysed every 10 samples to ensure minimal carryover between
analyses.</p>
</sec>
<sec id="Ch1.S3.SS6">
  <label>3.6</label><title>Data analysis</title>
      <p id="d1e1643">In order to characterise the hydrological behaviour of the drip sites, the
coefficient of variation (CV; Smart and Friederich, 1987; Baldini et al.,
2006) was calculated for discharge relative to the time of data collection
(CV % <inline-formula><mml:math id="M94" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M95" display="inline"><mml:mrow><mml:mi mathvariant="italic">σ</mml:mi><mml:mo>/</mml:mo><mml:mover accent="true"><mml:mi>u</mml:mi><mml:mo mathvariant="normal">‾</mml:mo></mml:mover><mml:mo>×</mml:mo><mml:mn mathvariant="normal">100</mml:mn></mml:mrow></mml:math></inline-formula>, with <inline-formula><mml:math id="M96" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula> being the standard deviation and <inline-formula><mml:math id="M97" display="inline"><mml:mover accent="true"><mml:mi>u</mml:mi><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:math></inline-formula> being the mean). Cross-correlation analysis between cumulative antecedent rainfall and drip rates was used to identify the response time of the drip sites to the rainfall amount during the monitoring period. Cluster analysis was employed to classify the drip sites according to hydrological similarities. Linear regressions were used to visualise the relationships between drip water <inline-formula><mml:math id="M98" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M99" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios, the cave air <inline-formula><mml:math id="M100" 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>, and cave air temperature as well as between rainfall amount and water isotopes. From these analyses a determination coefficient <inline-formula><mml:math id="M101" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M102" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> values were calculated; <inline-formula><mml:math id="M103" display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> values <inline-formula><mml:math id="M104" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 0.05 were considered to be statistically significant.</p>
</sec>
</sec>
<sec id="Ch1.S4">
  <label>4</label><title>Results</title>
<sec id="Ch1.S4.SS1">
  <label>4.1</label><title>Local meteorology</title>
      <p id="d1e1773">The available daily precipitation and temperature datasets from the stations
at Waipuna, Otorohanga Glenbrook, and Te Kuiti Ews show the same pattern
when overlapped, although the amplitudes differ (Fig. 3). The Waipuna
meteorological station records large variations in annual surface
temperature, with minimum and maximum temperatures ranging from
<inline-formula><mml:math id="M105" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.6</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M106" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in July to 33 <inline-formula><mml:math id="M107" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in January. Daily precipitation
ranged from 118 mm in May 2017 to 51 mm in December 2018, without any
pronounced seasonality. The driest months are typically November and
December (austral summer), and the wettest months are August and September.
While the variability and timing of rainfall at the three stations have the
same seasonal structure, the Waipuna rain station typically recorded higher
amounts. This is consistent with its higher altitude (<inline-formula><mml:math id="M108" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">90</mml:mn></mml:mrow></mml:math></inline-formula> m) relative to Otorohanga Glenbrook (40 m) and Te Kuiti Ews (62 m) and thus indicates an orographic effect on rainfall.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3" specific-use="star"><?xmltex \currentcnt{3}?><label>Figure 3</label><caption><p id="d1e1816">Daily precipitation from the Waipuna meteorological station (no data are available for October and November 2018 due to instrument failure) and the Otorohanga Glenbrook and Te Kuiti Ews stations (data from NIWA National
Climate Database, <uri>https://cliflo.niwa.co.nz/</uri>, last access: 26 June 2020).</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f03.png"/>

        </fig>

      <?pagebreak page3367?><p id="d1e1828"><?xmltex \hack{\newpage}?>The mean monthly surface conditions (2002–2019) from Te Kuiti Ews station
are shown in Fig. 4. These comprise monthly mean rainfall, monthly mean
temperature, potential evapotranspiration (PET), and effective rainfall (<inline-formula><mml:math id="M109" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">eff</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>), calculated as the difference between <inline-formula><mml:math id="M110" display="inline"><mml:mi>P</mml:mi></mml:math></inline-formula> and PET.</p>

      <?xmltex \floatpos{p}?><fig id="Ch1.F4"><?xmltex \currentcnt{4}?><label>Figure 4</label><caption><p id="d1e1853">Mean monthly temperature (red line), precipitation (blue line), and Priestley–Taylor potential evapotranspiration (PET) recorded at Te Kuiti
Ews station between 2002 and 2019 (green line) (<uri>https://cliflo.niwa.co.nz/</uri>, last access: 26 June 2020) and the difference between rainfall and PET (purple line). The shaded blue area represents the effective rainfall (<inline-formula><mml:math id="M111" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">eff</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>).</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f04.png"/>

        </fig>

</sec>
<sec id="Ch1.S4.SS2">
  <label>4.2</label><title>Waipuna Cave hydrology</title>
      <?pagebreak page3368?><p id="d1e1884">All drip sites were hydrologically active during the monitoring period, with
variable mean discharges between 10.5 and 22.1 <inline-formula><mml:math id="M112" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>L s<inline-formula><mml:math id="M113" 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>. The CV of the drip sites varied between 31 % and 149 % (Table 1). Cross-correlation analysis between antecedent cumulative rainfall and drip rate time series from the acoustic drip loggers show different lag times for each drip. These are 19 d for WP 1-1, 15 d for WP 1-2, 16 d for WP 1-3, and 4 d for WP-2 (Table 1; Fig. 5). For some drip sites, where drip rates were only measured manually during the cave visits, the observed lags were 18 d for WP 1-4 and WP 1A, 11 d for WP 1B and WP-3, and 6 d for
WP-4. Cluster analysis using manual and logger data reveals three main
groups of drip sites based on 25 observations of discharge at each drip site
with four common data points among them (Fig. 6). Based on the cluster analysis,
we identified three flow types, defined hereafter as type 1, which includes
drip sites with the slowest response to rainfall (WP 1-1, WP 1-2, WP 1-4, and
WP-4); type 2, which isolates drip WP-2 with the fastest response to
rainfall; and type 3, which includes drip sites WP 1-3 and WP-3 with
intermediate response time to rainfall. For comparison we have also located
the drip sites in the classification grid of Smart and Friederich (1987)
(Fig. S2), which will be discussed in Sect. 5.1.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5" specific-use="star"><?xmltex \currentcnt{5}?><label>Figure 5</label><caption><p id="d1e1909">Drip rates recorded by the loggers (red line) for the drip sites WP 1-1, WP 1-2, WP 1-3, and WP-2, plotted with their best fit of antecedent effective-rainfall days (blue). The date format in this figure is day/month/year.</p></caption>
          <?xmltex \igopts{width=369.885827pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f05.png"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6"><?xmltex \currentcnt{6}?><label>Figure 6</label><caption><p id="d1e1920">Results of cluster analysis of the drip site discharge time series, indicating the number of lag days calculated from the cross-correlation analysis. The grey cluster shows the drip site with the shortest lag to the antecedent rainfall (4 d); the blue cluster groups the drip sites with lag days between 11 and 16 d to antecedent rainfall; and the red cluster includes drip sites with a lag to antecedent rainfall between 15 and 24 d, with the exception of WP-4 (see main text).</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f06.png"/>

        </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><?xmltex \currentcnt{1}?><label>Table 1</label><caption><p id="d1e1933">Summary of drip site morphological characteristics, location in the
cave, response time to antecedent rainfall (values in bold were calculated
from the logger records, while the rest are from manual drip counts), coefficient of
variation as a percentage (CV), and hydrological behaviour.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="9">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis: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="left"/>
     <oasis:colspec colnum="9" colname="col9" align="center"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1">Drip</oasis:entry>
         <oasis:entry colname="col2">Description</oasis:entry>
         <oasis:entry colname="col3">Location</oasis:entry>
         <oasis:entry colname="col4">Height</oasis:entry>
         <oasis:entry colname="col5">Mean</oasis:entry>
         <oasis:entry colname="col6">Response</oasis:entry>
         <oasis:entry colname="col7">CV</oasis:entry>
         <oasis:entry colname="col8">Flow pattern</oasis:entry>
         <oasis:entry colname="col9">Type</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">site</oasis:entry>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4">to the</oasis:entry>
         <oasis:entry colname="col5">discharge</oasis:entry>
         <oasis:entry colname="col6">time to</oasis:entry>
         <oasis:entry colname="col7">(%)</oasis:entry>
         <oasis:entry colname="col8"/>
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4">ceiling</oasis:entry>
         <oasis:entry colname="col5">(<inline-formula><mml:math id="M114" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi></mml:mrow></mml:math></inline-formula>L s<inline-formula><mml:math id="M115" 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>)</oasis:entry>
         <oasis:entry colname="col6">rainfall</oasis:entry>
         <oasis:entry colname="col7"/>
         <oasis:entry colname="col8"/>
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4">(m)</oasis:entry>
         <oasis:entry colname="col5"/>
         <oasis:entry colname="col6">(d)</oasis:entry>
         <oasis:entry colname="col7"/>
         <oasis:entry colname="col8"/>
         <oasis:entry colname="col9"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">WP 1-1</oasis:entry>
         <oasis:entry colname="col2">Part of the flowstone curtain</oasis:entry>
         <oasis:entry colname="col3">Organ Loft</oasis:entry>
         <oasis:entry colname="col4">6</oasis:entry>
         <oasis:entry colname="col5">63.35</oasis:entry>
         <oasis:entry colname="col6">17</oasis:entry>
         <oasis:entry colname="col7">52.9</oasis:entry>
         <oasis:entry colname="col8">Diffuse flow</oasis:entry>
         <oasis:entry colname="col9">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP 1-2</oasis:entry>
         <oasis:entry colname="col2">Part of the flowstone curtain</oasis:entry>
         <oasis:entry colname="col3">Organ Loft</oasis:entry>
         <oasis:entry colname="col4">6</oasis:entry>
         <oasis:entry colname="col5">43.74</oasis:entry>
         <oasis:entry colname="col6">15</oasis:entry>
         <oasis:entry colname="col7">85.1</oasis:entry>
         <oasis:entry colname="col8">Diffuse flow</oasis:entry>
         <oasis:entry colname="col9">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP 1-3</oasis:entry>
         <oasis:entry colname="col2">Part of the flowstone curtain</oasis:entry>
         <oasis:entry colname="col3">Organ Loft</oasis:entry>
         <oasis:entry colname="col4">6</oasis:entry>
         <oasis:entry colname="col5">105.57</oasis:entry>
         <oasis:entry colname="col6">16</oasis:entry>
         <oasis:entry colname="col7">56.2</oasis:entry>
         <oasis:entry colname="col8">Diffuse flow</oasis:entry>
         <oasis:entry colname="col9">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP 1-4</oasis:entry>
         <oasis:entry colname="col2">Part of the flowstone curtain</oasis:entry>
         <oasis:entry colname="col3">Organ Loft</oasis:entry>
         <oasis:entry colname="col4">6</oasis:entry>
         <oasis:entry colname="col5">22.13</oasis:entry>
         <oasis:entry colname="col6">18</oasis:entry>
         <oasis:entry colname="col7">53.9</oasis:entry>
         <oasis:entry colname="col8">Diffuse flow</oasis:entry>
         <oasis:entry colname="col9">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP 1A</oasis:entry>
         <oasis:entry colname="col2">Part of the flowstone curtain</oasis:entry>
         <oasis:entry colname="col3">Organ Loft</oasis:entry>
         <oasis:entry colname="col4">6</oasis:entry>
         <oasis:entry colname="col5">83.99</oasis:entry>
         <oasis:entry colname="col6">18</oasis:entry>
         <oasis:entry colname="col7">36.3</oasis:entry>
         <oasis:entry colname="col8">Diffuse flow</oasis:entry>
         <oasis:entry colname="col9">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP 1B</oasis:entry>
         <oasis:entry colname="col2">Part of the flowstone curtain</oasis:entry>
         <oasis:entry colname="col3">Organ Loft</oasis:entry>
         <oasis:entry colname="col4">6</oasis:entry>
         <oasis:entry colname="col5">51.83</oasis:entry>
         <oasis:entry colname="col6">11</oasis:entry>
         <oasis:entry colname="col7">48.2</oasis:entry>
         <oasis:entry colname="col8">Combined flow</oasis:entry>
         <oasis:entry colname="col9">3</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP FB</oasis:entry>
         <oasis:entry colname="col2">Flowstone bottom</oasis:entry>
         <oasis:entry colname="col3">Organ Loft</oasis:entry>
         <oasis:entry colname="col4">8</oasis:entry>
         <oasis:entry colname="col5">30.08</oasis:entry>
         <oasis:entry colname="col6">9</oasis:entry>
         <oasis:entry colname="col7">81.8</oasis:entry>
         <oasis:entry colname="col8">Diffuse flow</oasis:entry>
         <oasis:entry colname="col9">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP-2</oasis:entry>
         <oasis:entry colname="col2">Independent stalactite</oasis:entry>
         <oasis:entry colname="col3">Upper gallery</oasis:entry>
         <oasis:entry colname="col4">9</oasis:entry>
         <oasis:entry colname="col5">59.57</oasis:entry>
         <oasis:entry colname="col6">4</oasis:entry>
         <oasis:entry colname="col7">149.4</oasis:entry>
         <oasis:entry colname="col8">Fracture flow</oasis:entry>
         <oasis:entry colname="col9">2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP-3</oasis:entry>
         <oasis:entry colname="col2">Independent stalactite</oasis:entry>
         <oasis:entry colname="col3">Upper gallery</oasis:entry>
         <oasis:entry colname="col4">9</oasis:entry>
         <oasis:entry colname="col5">91.62</oasis:entry>
         <oasis:entry colname="col6">11</oasis:entry>
         <oasis:entry colname="col7">31.3</oasis:entry>
         <oasis:entry colname="col8">Combined flow</oasis:entry>
         <oasis:entry colname="col9">3</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">WP-4</oasis:entry>
         <oasis:entry colname="col2">Independent stalactite</oasis:entry>
         <oasis:entry colname="col3">Upper gallery</oasis:entry>
         <oasis:entry colname="col4">12</oasis:entry>
         <oasis:entry colname="col5">32.07</oasis:entry>
         <oasis:entry colname="col6">6</oasis:entry>
         <oasis:entry colname="col7">53.2</oasis:entry>
         <oasis:entry colname="col8">Fracture flow</oasis:entry>
         <oasis:entry colname="col9">2</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup>

</oasis:table><?xmltex \hack{\vspace*{5mm}}?></table-wrap>

</sec>
<sec id="Ch1.S4.SS3">
  <label>4.3</label><title>Isotope geochemistry</title>
      <p id="d1e2414">Drip water oxygen isotope values varied between <inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3.0</mml:mn></mml:mrow></mml:math></inline-formula> ‰ and <inline-formula><mml:math id="M117" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2.4</mml:mn></mml:mrow></mml:math></inline-formula> ‰ for <inline-formula><mml:math id="M118" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.8</mml:mn></mml:mrow></mml:math></inline-formula> ‰ and <inline-formula><mml:math id="M120" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.2</mml:mn></mml:mrow></mml:math></inline-formula> ‰ for <inline-formula><mml:math id="M121" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M122" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">32.7</mml:mn></mml:mrow></mml:math></inline-formula> ‰ and <inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">28.3</mml:mn></mml:mrow></mml:math></inline-formula> ‰ for <inline-formula><mml:math id="M124" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>. The d-excess value ranged from 8.8 ‰ to 15.4 ‰ (Fig. S6). All drip water <inline-formula><mml:math id="M125" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M126" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> values fall on the local meteoric water line (LMWL; <inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">7.15</mml:mn><mml:mo>⋅</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mo>+</mml:mo><mml:mn mathvariant="normal">7.6</mml:mn></mml:mrow></mml:math></inline-formula>) as determined from rainwater samples from the Waikato region in the North Island (Fig. 7; Keller et al., 2014). A linear regression of all drip waters is expressed as <inline-formula><mml:math id="M128" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">5.05</mml:mn><mml:mo>⋅</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2.3</mml:mn></mml:mrow></mml:math></inline-formula>. The very low intercept of <inline-formula><mml:math id="M129" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2.3</mml:mn></mml:mrow></mml:math></inline-formula> is the result of the very narrow range of the drip water cluster and is not related to secondary evaporation. The <inline-formula><mml:math id="M130" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values of the cave stream are in the same range as the drip waters, but <inline-formula><mml:math id="M131" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> values are <inline-formula><mml:math id="M132" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">20</mml:mn></mml:mrow></mml:math></inline-formula> ‰ higher (<inline-formula><mml:math id="M133" display="inline"><mml:mrow><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">5.9</mml:mn><mml:mo>⋅</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mo>+</mml:mo><mml:mn mathvariant="normal">3.4</mml:mn></mml:mrow></mml:math></inline-formula>). The d-excess value of the stream water ranged from 9.4 ‰ to 15 ‰.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7"><?xmltex \currentcnt{7}?><label>Figure 7</label><caption><p id="d1e2671">Cross plot of <inline-formula><mml:math id="M134" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> versus <inline-formula><mml:math id="M135" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in drip water (pink circles), the Waikato region precipitation (blue triangles), and Waipuna stream (green diamonds). All cave waters fall in a very narrow range (inset) and within error on the local meteoric water line (blue line; Keller et al., 2014). The cross in the inset shows the 2<inline-formula><mml:math id="M136" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula> uncertainties for <inline-formula><mml:math id="M137" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M138" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f07.png"/>

        </fig>

      <p id="d1e2733">All drip water <inline-formula><mml:math id="M139" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M140" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values fall close to the GMWL (Fig. S3), the equation for which is <inline-formula><mml:math id="M141" display="inline"><mml:mrow><mml:mi>ln⁡</mml:mi><mml:mo>(</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1000</mml:mn><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.528</mml:mn><mml:mi>ln⁡</mml:mi><mml:mo>(</mml:mo><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow><mml:mo>/</mml:mo><mml:mn mathvariant="normal">1000</mml:mn><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mn mathvariant="normal">0.00033</mml:mn></mml:mrow></mml:math></inline-formula> (Luz and Barkan, 2010). The mean <inline-formula><mml:math id="M142" display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O deviation with respect to the
GMWL (<inline-formula><mml:math id="M143" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>) in the drip water is <inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:mn mathvariant="normal">26</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">8</mml:mn></mml:mrow></mml:math></inline-formula> per meg, with the
values ranging from 6 to 44 per meg. The <inline-formula><mml:math id="M145" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values of the
cave stream were <inline-formula><mml:math id="M146" display="inline"><mml:mrow><mml:mn mathvariant="normal">25</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> per meg on average.</p>
      <p id="d1e2888">Between September 2016 and June 2017, drip sites WP 1-1, WP 1-2, WP 1-3, WP 1-4, WP 1A, and WP 1B showed low variability in drip water <inline-formula><mml:math id="M147" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M148" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>, with ranges of 0.5 ‰ (<inline-formula><mml:math id="M149" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.4</mml:mn></mml:mrow></mml:math></inline-formula> ‰ to <inline-formula><mml:math id="M150" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.9</mml:mn></mml:mrow></mml:math></inline-formula> ‰) in <inline-formula><mml:math id="M151" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and 3.9 ‰ (<inline-formula><mml:math id="M152" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">28.8</mml:mn></mml:mrow></mml:math></inline-formula> ‰ to <inline-formula><mml:math id="M153" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">32.7</mml:mn></mml:mrow></mml:math></inline-formula> ‰) in <inline-formula><mml:math id="M154" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> and mean values of <inline-formula><mml:math id="M155" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.61</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.04</mml:mn></mml:mrow></mml:math></inline-formula> ‰ (2<inline-formula><mml:math id="M156" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) and <inline-formula><mml:math id="M157" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">31.01</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.4</mml:mn></mml:mrow></mml:math></inline-formula> ‰, respectively. Although small, this range is still
greater than the analytical error of 0.16 ‰ and 1.4 ‰, respectively (Figs. 8b–c and S4). From July 2017 to January 2019 virtually no variability was observed in <inline-formula><mml:math id="M158" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M159" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> (Figs. 8b–c and S4). The drip water <inline-formula><mml:math id="M160" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M161" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> in that period have ranges of 0.3 ‰ (<inline-formula><mml:math id="M162" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.4</mml:mn></mml:mrow></mml:math></inline-formula> ‰ to <inline-formula><mml:math id="M163" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.7</mml:mn></mml:mrow></mml:math></inline-formula> ‰) in <inline-formula><mml:math id="M164" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and 2.16 ‰ (<inline-formula><mml:math id="M165" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">29.2</mml:mn></mml:mrow></mml:math></inline-formula> ‰ to <inline-formula><mml:math id="M166" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">31.3</mml:mn></mml:mrow></mml:math></inline-formula> ‰) in <inline-formula><mml:math id="M167" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>, with mean values of
<inline-formula><mml:math id="M168" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.61</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula> ‰ (2<inline-formula><mml:math id="M169" display="inline"><mml:mi mathvariant="italic">σ</mml:mi></mml:math></inline-formula>) and <inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">30.47</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">0.18</mml:mn></mml:mrow></mml:math></inline-formula> ‰. This range is virtually at the analytical uncertainty level.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8" specific-use="star"><?xmltex \currentcnt{8}?><label>Figure 8</label><caption><p id="d1e3162">Drip water <inline-formula><mml:math id="M171" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> time series of all drips grouped
according to the three main response lags (5, 18, and 24 d) to antecedent
rainfall (AR) at Otorohanga Glenbrook station (blue vertical bars). <bold>(a)</bold> Drip sites WP-2, WP-3, and WP-4 (5 d antecedent rainfall). <bold>(b)</bold> Drip sites from the flowstone curtain, WP 1-1, WP 1-4, and WP 1B (18 d antecedent rainfall). <bold>(c)</bold> Drip sites from the flowstone curtain, WP 1-2, WP 1-3, and WP 1A (24 d antecedent rainfall). The Otorohanga rainfall record covers the period between September 2016 and January 2019; no data are available for October and November 2018. The date format in this figure is day/month/year.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f08.png"/>

        </fig>

      <p id="d1e3193">By contrast, the three drip sites with the shortest lags, WP-2, WP-3, and
WP-4, exhibit higher variability in <inline-formula><mml:math id="M172" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M173" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula>. In particular, sites WP-2 and WP-3 show a marked increase (0.5 ‰) in <inline-formula><mml:math id="M174" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> between December 2016 and January 2017 (Fig. 8a). <inline-formula><mml:math id="M175" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> varies in the same way as <inline-formula><mml:math id="M176" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> (Fig. S5).</p>
</sec>
<sec id="Ch1.S4.SS4">
  <label>4.4</label><title>Drip water major and trace elements</title>
      <p id="d1e3266">Here we report elemental composition data for those components typically
influenced by PCP, i.e. Ca concentration (Fairchild et al., 2000) and <inline-formula><mml:math id="M177" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M178" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios (Tremaine et al., 2016). Drip water Ca concentrations range from 0.7 to 2.2 mol L<inline-formula><mml:math id="M179" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>; <inline-formula><mml:math id="M180" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> varied from 17.7 to 66.5; and <inline-formula><mml:math id="M181" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> varied from 0.24 to 1.11 (mmol mol<inline-formula><mml:math id="M182" 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>). All drip sites show a strong positive correlation between <inline-formula><mml:math id="M183" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M184" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios, with coefficients of determination varying from 0.68 to 0.9 (Fig. 10b). The two different trends observed in the relationship between <inline-formula><mml:math id="M185" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M186" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios will be
discussed in Sect. 5.5. The temporal variability of the <inline-formula><mml:math id="M187" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M188" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios shows three noticeable peaks for all drip sites during the summers of 2017 (February), 2018 (January), and 2019 after the previously reduced effective rainfall. Drip waters collected during late summer
(January–February) generally had higher <inline-formula><mml:math id="M189" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M190" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios and lower Ca concentrations, while samples collected in winter (July–August) had the lowest <inline-formula><mml:math id="M191" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M192" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios and the highest Ca concentrations (Figs. 11 and S7).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F9" specific-use="star"><?xmltex \currentcnt{9}?><label>Figure 9</label><caption><p id="d1e3465">Drip water <inline-formula><mml:math id="M193" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> time series of all drips grouped
according to the three main response lags (5, 18, and 24 d) to antecedent
rainfall (AR) at Otorohanga Glenbrook station (blue vertical bars). <bold>(a)</bold> Drip sites WP-2, WP-3, and WP-4 (5 d antecedent rainfall). <bold>(b)</bold> Drip sites from the flowstone curtain, WP 1-1, WP 1-4, and WP 1B (18 d antecedent rainfall). <bold>(c)</bold> Drip sites from the flowstone curtain, WP 1-2, WP 1-3, and WP 1A (24 d antecedent rainfall). The Otorohanga rainfall record covers the period between September 2016 and January 2019; no data are available for October and November 2018. The date format in this figure is day/month/year.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f09.png"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F10" specific-use="star"><?xmltex \currentcnt{10}?><label>Figure 10</label><caption><p id="d1e3500">Waipuna Cave drip waters sampled during the monitoring period
October 2016 to January 2019. <bold>(a)</bold> Ca concentration versus <inline-formula><mml:math id="M194" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios. <bold>(b)</bold> <inline-formula><mml:math id="M195" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> versus <inline-formula><mml:math id="M196" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M197" 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="M198" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>. The orange symbols correspond to diffuse flow drip sites and blue symbols signify fracture flow drip sites. The two different trends evident in the relationship between <inline-formula><mml:math id="M199" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M200" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> will be discussed in Sect. 5.5.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f10.png"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F11" specific-use="star"><?xmltex \currentcnt{11}?><label>Figure 11</label><caption><p id="d1e3606">Drip water <inline-formula><mml:math id="M201" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios time series of all drips grouped according to the three main response lags (5, 18, and 24 d) to antecedent rainfall (AR) at Otorohanga Glenbrook station (blue vertical bars). <bold>(a)</bold> Drip sites WP-2, WP-3, and WP-4 (5 d antecedent rainfall). <bold>(b)</bold> Drip sites from the flowstone curtain, WP 1-1, WP 1-4, and WP 1B (18 d antecedent rainfall). <bold>(c)</bold> Drip sites from the flowstone curtain, WP 1-2, WP 1-3, and WP 1A (24 d antecedent rainfall). The Otorohanga rainfall record covers the period between September 2016 and January 2019; no data are available for October and November 2018. The date format in this figure is day/month/year.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f11.png"/>

        </fig>

</sec>
<sec id="Ch1.S4.SS5">
  <label>4.5</label><?xmltex \opttitle{Cave air temperature and {$\protect\chem{CO_{{2}}}$}}?><title>Cave air temperature and <inline-formula><mml:math id="M202" 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></title>
      <p id="d1e3656">Daily cave air temperature in the Organ Loft chamber recorded between June 2017 and May 2018 varied between 7.4 and 11.7 <inline-formula><mml:math id="M203" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C (mean 10.4 <inline-formula><mml:math id="M204" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C; Fig. 12a and b), with the highest temperatures measured in summer (February and March) and the lowest temperatures in winter (July and August). The air temperature logger at the Waipuna Cave meteorological station recorded temperatures between <inline-formula><mml:math id="M205" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.6</mml:mn></mml:mrow></mml:math></inline-formula> and 29.3 <inline-formula><mml:math id="M206" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. The temperature difference (<inline-formula><mml:math id="M207" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>T</mml:mi></mml:mrow></mml:math></inline-formula>) between Waipuna Cave air and the external air shows an annual cycle (Fig. 12c), ranging from <inline-formula><mml:math id="M208" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">22</mml:mn></mml:mrow></mml:math></inline-formula> to 8.3 <inline-formula><mml:math id="M209" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, with a mean of <inline-formula><mml:math id="M210" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2.1</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M211" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. The largest negative <inline-formula><mml:math id="M212" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>T</mml:mi></mml:mrow></mml:math></inline-formula> values occurred from late spring in November 2017 to early autumn in April 2017 owing to the marked increase in external temperature.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F12"><?xmltex \currentcnt{12}?><label>Figure 12</label><caption><p id="d1e3757">Comparison of meteorological parameters. <bold>(a)</bold> Daily mean air
temperature at Waipuna station and in Waipuna Cave (in the Organ Loft chamber).
<bold>(b)</bold> Manual cave air <inline-formula><mml:math id="M213" 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> concentrations and daily mean air temperature in the Organ Loft chamber. <bold>(c)</bold> Calculated temperature difference <inline-formula><mml:math id="M214" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>T</mml:mi></mml:mrow></mml:math></inline-formula> between cave air and surface air from June to May 2018. During winter, the cave is warmer, and during summer, the cave is colder compared to the surface air.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f12.png"/>

        </fig>

      <p id="d1e3796">Cave air <inline-formula><mml:math id="M215" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> varied from a minimum of 438 ppm in September 2016 to a maximum of 930 ppm recorded in March 2019 (Fig. 12b). Cave air <inline-formula><mml:math id="M216" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is positively correlated with cave air temperature (<inline-formula><mml:math id="M217" 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">0.67</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M218" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.045</mml:mn></mml:mrow></mml:math></inline-formula>). The highest air <inline-formula><mml:math id="M219" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> values are registered when cave air temperature reaches its maximum in summer and decrease when cave air temperature is lowest in winter (see the discussion in Sect. 5.4).</p>
</sec>
</sec>
<sec id="Ch1.S5">
  <label>5</label><title>Discussion</title>
      <p id="d1e3875">This work aims at evaluating the hydrochemical response of Waipuna Cave to
environmental dynamics and to test its suitability for speleothem-based
palaeo-climate reconstructions. We explore the links between the
physiochemical parameters measured in Waipuna Cave and rainfall and
temperature changes at seasonal to inter-annual timescales. Our results show
that Waipuna Cave reflects the external environmental dynamics on
inter-annual timescales. The results and interpretation of monitoring data
constitute a solid platform for the interpretation of speleothem-based
reconstructions that are ongoing.</p><?xmltex \hack{\newpage}?>
<?pagebreak page3370?><sec id="Ch1.S5.SS1">
  <label>5.1</label><title>Waipuna Cave hydrology</title>
      <p id="d1e3886">The meteorological data from the Otorohanga Glenbrook and Te Kuiti Ews stations
are considered suitable for evaluating the Waipuna Cave monitoring data,
given the rainfall patterns are similar to those at Waipuna. The monitored
drip sites in Waipuna Cave are highly sensitive to rainfall variability,
demonstrating the permeability of the overlying soil and the relatively thin
bedrock overburden.</p>
      <p id="d1e3889"><?xmltex \hack{\newpage}?>Our results indicate that the monitored drip sites respond to three
different infiltration pathways: (i) type 1 – diffuse flow, (ii) type 2 – fracture flow, and (iii) type 3 – combined flow. Type 1 drips WP 1-1, WP 1-2, WP 1-4, and WP 1A show the slowest response to rainfall (lagging between 11 and 19 d).
These drips belong to the Organ Loft curtain, which strongly supports the
hypothesis that these sites are hydrologically connected to each other.
Given that the curtain is part of the continuum from the ceiling to the
floor (ca. 6 m height), it is likely that all its drip sites are mainly fed
by diffuse flow through the limestone matrix, which is a function of the
primary porosity of the karst (Bradley et al., 2010). Type 2 is represented
by drip sites WP-2 and WP-4, which are located in the upper gallery of the
Organ Loft with a higher ceiling. These drips have a faster response (4 to 6 d) to antecedent rainfall, suggesting that these drips are controlled
mainly by fracture flow. This is consistent with the clear identification of
zones of structural weakness along the ceiling (physically representing
fault- or joint-like structures) and the shorter vadose flow path at these
locations. The cross-correlation of the antecedent rainfall and the drip
rates agrees with the cluster output for all drip sites except drip site WP-4, which has a response time of 4 d but clusters with the group of
drip sites with a lag of 18 to 24 d. This can be explained by the limited
size of the dataset: the drip rates of WP-4 were measured only manually,
thus limiting the input for the cluster analysis compared to drip sites
monitored with loggers. Finally, we grouped WP 1-3 and WP-3 into flow type 3 because these two drip sites have similar intermediate response rates to
rainfall (11 d), independent of their location in the Organ Loft chamber,
which is in the ceiling of the upper gallery for WP-3 and the flowstone
curtain for WP 1-3. It is likely that these drips are fed by a combination
of fracture and matrix flow (Mahmud et al., 2018).</p>
      <p id="d1e3893">Although the response time varies from days to 2–3 weeks, all drip sites
forming stalagmites and feeding the flowstone reflect precipitation dynamics
at a sub-annual scale. The three types of drip discharge in Waipuna Cave do
not satisfactorily fit into the classification model of Smart and Friederich (1987), which locates drip sites WP 1A, WP 1B, and WP-3 fall in the seepage flow and sites WP 1-1, WP 1-2, WP 1-3, WP 1-4, WP FB, WP-4, and WP-2 in the fracture flow range (Fig. S2).</p>
</sec>
<sec id="Ch1.S5.SS2">
  <label>5.2</label><title>Rainwater isotope geochemistry</title>
      <p id="d1e3904">The distribution of the rainwater oxygen and hydrogen isotopes along the
LMWL (Fig. 7) does not reveal a clear seasonal pattern. However, when
comparing rainfall <inline-formula><mml:math id="M220" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values with the amount of precipitation across the entire monitoring period (Fig. 13, black line), we observe a positive relationship (<inline-formula><mml:math id="M221" 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">0.56</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M222" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.0001</mml:mn></mml:mrow></mml:math></inline-formula>). The strongest correlations between rainfall amount and <inline-formula><mml:math id="M223" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values are observed in austral spring and summer (<inline-formula><mml:math id="M224" 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">0.68</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M225" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.0002</mml:mn></mml:mrow></mml:math></inline-formula> and
<inline-formula><mml:math id="M226" 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">0.89</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M227" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.0001</mml:mn></mml:mrow></mml:math></inline-formula>, respectively) when temperature is highest in the Waikato area (Fig. 13, green and orange lines). Among the various climatic and geographical effects on the isotopic composition of rainwater, the “amount effect” has been shown to significantly influence rainwater
<inline-formula><mml:math id="M228" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in sub-tropical regions. The amount effect is the
empirical negative correlation between rainfall amount and rainwater <inline-formula><mml:math id="M229" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> (Dansgaard, 1964) which arises from the partial re-evaporation and thus isotopic enrichment of rain droplets falling through relatively dry air below cloud level during periods of reduced precipitation (Dansgaard, 1964; Risi et al., 2008; Lachniet, 2009; Breitenbach et al., 2010). This process affects the isotopic signature in rainfall observed in the Waitomo region in spring and summer but not during the winter season when re-evaporation from falling rain is minimal due to high relative humidity (this is reflected in lower <inline-formula><mml:math id="M230" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> value<?pagebreak page3373?> samples from April to September; Fig. 13). In the wet season, rain droplets are less affected by re-evaporation and remain unaltered with respect to <inline-formula><mml:math id="M231" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>. These observations suggest that regional atmospheric conditions, associated with ENSO dynamics or the strength of the Westerlies, can impose their signature on the isotopic composition of precipitation.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F13"><?xmltex \currentcnt{13}?><label>Figure 13</label><caption><p id="d1e4070">Cross plot of precipitation amount versus <inline-formula><mml:math id="M232" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> in
rainfall for the period August 2007 to December 2009 from the Waikato region
(data source: Keller et al., 2014). The black line indicates the correlation if all data are considered, while the coloured symbols and regressions relate to the different seasons.</p></caption>
          <?xmltex \igopts{width=170.716535pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f13.png"/>

        </fig>

      <p id="d1e4092">Drip water <inline-formula><mml:math id="M233" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M234" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> values closely reflect the mean isotopic composition of the rainwater (Fig. 7). The isotope signatures of drip waters from the Organ Loft curtain lack seasonal patterns, as they are
decoupled from recharge rates by a significant epikarst store (Figs. 8b–c
and S4c). Instead, homogenisation in the epikarst reservoir controls the
isotopic composition of the water feeding the Organ Loft curtain. As
highlighted in Fig. 7, <inline-formula><mml:math id="M235" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values vary minimally around a
mean drip water <inline-formula><mml:math id="M236" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> value of <inline-formula><mml:math id="M237" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.6</mml:mn></mml:mrow></mml:math></inline-formula> ‰, which is only slightly lower than the average rainwater value (<inline-formula><mml:math id="M238" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.15</mml:mn></mml:mrow></mml:math></inline-formula> ‰; Keller et al., 2014). This similarity indicates the rapid mixing of freshly infiltrating water with older water in the epikarst, as also found in earlier studies from the Waitomo district (Williams and Fowler, 2002) and elsewhere (Mattey et al., 2008; Tremaine et al., 2016; Breitenbach et al., 2019). The observed buffering of drip water towards the mean rainwater <inline-formula><mml:math id="M239" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> value suggests that speleothem <inline-formula><mml:math id="M240" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> ratios can be expected to reflect multi-annual to multi-decadal changes in rainfall isotope geochemical patterns. Furthermore, it may be possible that speleothems from Waipuna Cave record a long-term temperature signal that is unbiased with regard to seasonal infiltration changes. On the other hand, this pattern might also indicate that Waipuna Cave speleothem isotope geochemistry is insensitive to sub-seasonal changes in rainfall <inline-formula><mml:math id="M241" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M242" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> ratios. Flowstone <inline-formula><mml:math id="M243" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values originating from water from these drips are unlikely to reflect atmospheric dynamics related to seasonal or ENSO variability, and other proxies must be used instead to identify these dynamics.</p>
      <p id="d1e4228">Waipuna Cave drip waters do not show significant variations in <inline-formula><mml:math id="M244" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> over time, and most results overlap within analytical
errors (Fig. 9). Recent investigations into triple oxygen isotopes in
midlatitude rainfall have reported seasonal oscillations in
<inline-formula><mml:math id="M245" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> that have been attributed to changes in relative
humidity at the moisture source (i.e. where the water vapour originates)
or to swings between different moisture sources with evaporation occurring
under different environmental conditions (Affolter et al., 2015; Uechi and
Uemura, 2019). Unlike the d-excess parameter, <inline-formula><mml:math id="M246" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in rainfall is
apparently almost exclusively controlled by relative humidity at the
water-vapour boundary layer (i.e. the interface between water and free
atmosphere), with insignificant temperature effects (Luz and Barkan, 2010).
Thus, if there are seasonal changes in the dominant moisture source and
origin of storms for the Waikato area, these would be likely to affect local
precipitation and this variability could be recorded in Waipuna Cave
drip water. However, no significant variations in <inline-formula><mml:math id="M247" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are
found over the studied<?pagebreak page3374?> period (September 2017 to October 2018), suggesting
that the isotope values of meteoric water are homogenised in the epikarst
and that Waipuna Cave drip water <inline-formula><mml:math id="M248" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is insensitive to
(sub-)seasonal changes. We suspect that, as with <inline-formula><mml:math id="M249" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> ratios,
the interannual response of cave drip water might be controlled by long-term
variations in the <inline-formula><mml:math id="M250" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> of rainfall and changes in the
relative importance of ENSO and the Southern Westerlies. However, given that the
narrow range of <inline-formula><mml:math id="M251" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in rainwater in the midlatitudes
(normally <inline-formula><mml:math id="M252" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">30</mml:mn></mml:mrow></mml:math></inline-formula> per meg; Luz and Barkan, 2010) and the relatively large errors of current analytical methods (i.e. <inline-formula><mml:math id="M253" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">8</mml:mn></mml:mrow></mml:math></inline-formula> per meg), longer (i.e. multi-decadal) drip water monitoring would be needed to test this hypothesis.</p>
      <p id="d1e4370">The fracture-flow-fed drip sites WP-2, WP-3, and WP-4 are more sensitive to
variations in surface conditions and were likely affected by a moderate
drought in the summer of 2016–2017 (Fig. 8a). 2016 was the warmest year on
record for New Zealand, with average annual temperatures 0.5 to
1.2 <inline-formula><mml:math id="M254" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C above normal (NIWA annual climate summary; NIWA, 2016a). Rainfall was 50 %–79 % below average in December 2016, causing anomalously low soil moisture levels (NIWA summer 2016–2017 report; NIWA, 2016b). Hence the January 2017 <inline-formula><mml:math id="M255" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> values of <inline-formula><mml:math id="M256" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.08</mml:mn></mml:mrow></mml:math></inline-formula> ‰ and <inline-formula><mml:math id="M257" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5.12</mml:mn></mml:mrow></mml:math></inline-formula> ‰ (Fig. 8a) might have been affected by the reduced infiltration caused by the higher evapotranspiration relative to precipitation.</p>
      <p id="d1e4415">The rapid decrease in drip water <inline-formula><mml:math id="M258" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> at the fast drip sites in
March and April 2017 could have been caused by aquifer recharge (Fig. 8a).
The decrease coincides with a period of increased precipitation, which would
have quickly infiltrated the relatively dry soil and entered the aquifer.
This is consistent with the short water residence time of 5 d and the
greater degree of fracture flow and vadose zone influence at these sites
compares with the slower drip sites.</p>
</sec>
<sec id="Ch1.S5.SS3">
  <label>5.3</label><title>Drip water major and trace elements</title>
      <p id="d1e4440">Detecting short-term (sub-seasonal to annual) hydrological changes related
to environmental conditions above Waipuna Cave requires sensitive (and
ideally quantitative) proxies. In the following, we review the parameters we
have measured in terms of their sensitivity.</p>
      <p id="d1e4443">Negative effective precipitation (<inline-formula><mml:math id="M259" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">eff</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>), either from reduced rainfall or enhanced PET, can enhance the degassing of <inline-formula><mml:math id="M260" 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> from the epikarst zone and thus prior calcite precipitation (PCP) in the epikarst (Fairchild et al., 2000). Another factor potentially controlling PCP is cave ventilation. Enhanced ventilation removes moisture and <inline-formula><mml:math id="M261" 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> from the cave environment, which can result in <inline-formula><mml:math id="M262" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">100</mml:mn></mml:mrow></mml:math></inline-formula> % relative humidity (RH)
and/or near-atmospheric <inline-formula><mml:math id="M263" 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> concentrations in cave air (Gázquez et al., 2016). Low cave air RH values can lead to drip water evaporation, while low cave air <inline-formula><mml:math id="M264" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> can enhance drip water degassing and the formation of speleothems at the cave ceiling. Both processes can affect <inline-formula><mml:math id="M265" display="inline"><mml:mrow><mml:mi>X</mml:mi><mml:mo>/</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:mrow></mml:math></inline-formula> and stable isotope ratios (Fairchild et al., 2006a; Breitenbach et al., 2015). Normally, the processes in the epikarst and in the cave act in concert and cannot be disentangled. Here, we show that detailed monitoring of <inline-formula><mml:math id="M266" display="inline"><mml:mrow><mml:mi>X</mml:mi><mml:mo>/</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:mrow></mml:math></inline-formula> dynamics in drip water can give valuable insights into the relative importance of these two zones, namely the epikarst and cave itself, for PCP intensity.</p>
      <p id="d1e4540">The PCP predictor line represents the modelled evolution of the <inline-formula><mml:math id="M267" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">Ca</mml:mi><mml:mi mathvariant="normal">aq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
concentration which precipitates calcite in equilibrium as <inline-formula><mml:math id="M268" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> decreases from the soil to the cave (Fairchild et al., 2006b). The <inline-formula><mml:math id="M269" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios of Waipuna Cave drip waters closely follow the PCP predictor line (Fig. 10a). <inline-formula><mml:math id="M270" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M271" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios are plotted in Fig. 10b, and a strong positive correlation is observed in Waipuna Cave drip waters (<inline-formula><mml:math id="M272" 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="M273" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>; Sinclair et al., 2012; Tremaine and Froelich, 2013). This effect has also been widely identified in cave systems in Australia, with a climate similar to the Waitomo region. For example, Harrie Wood Cave (35<inline-formula><mml:math id="M274" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>44<inline-formula><mml:math id="M275" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> S, 148<inline-formula><mml:math id="M276" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>30<inline-formula><mml:math id="M277" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula> E) drip water <inline-formula><mml:math id="M278" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M279" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios show enhanced PCP during dry periods associated with El Niño and reduced PCP during La Niña events (Tadros et al., 2016).</p>
      <p id="d1e4694">The degree of PCP could be expected to be linked to infiltration rates, with
fracture flow being prone to more PCP because it empties faster compared to
seepage flow. As long as the epikarst remains water-filled, PCP would be
minimised, whereas the fast drying of the epikarst results in the intrusion of soil
air, which might induce PCP. The fracture-flow-fed drips can be distinguished
from seepage-flow-fed ones by lower Ca concentrations and increased scatter
around the predicted PCP line (Fig. 10a). This can be explained by somewhat
shorter interaction between the infiltrating water and the host rock. When
comparing the elemental composition of the different drip sites (Fig. 10b),
we observe that all drips show comparable <inline-formula><mml:math id="M280" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M281" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios, suggesting that all drips are similarly affected by PCP. The different infiltration lag time of the individual drips thus does not appear to affect the extent of PCP in Waipuna Cave.</p>
      <p id="d1e4722">Although rainfall is evenly distributed throughout the year, a strong
seasonal PCP signal is found in the drip water for all drip sites across the
whole monitoring period (Fig. 11). Lower <inline-formula><mml:math id="M282" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M283" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios occurred in the wettest months, when precipitation exceeded evapotranspiration. Conversely, higher <inline-formula><mml:math id="M284" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M285" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios are found in the driest months (i.e. November to March), when the potential evapotranspiration exceeds rainfall and effective infiltration is negative (Figs. 11 and S7). Hydrological changes thus govern epikarst PCP, which in turn controls drip water <inline-formula><mml:math id="M286" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M287" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios (Fig. 10b). This observation supports our hypothesis that Waipuna Cave drip waters are capable of registering changes in local hydrology, with seasonal differences being most strongly expressed in <inline-formula><mml:math id="M288" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios. Changes in the <inline-formula><mml:math id="M289" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratio potentially reflect the interplay of PCP and enhanced selective Sr leaching (incongruent dissolution), which both operate to increase <inline-formula><mml:math id="M290" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> in the drier months (Sinclair et al., 2012), while
the wetter months are<?pagebreak page3375?> characterised by infiltration and reduced selective Sr leaching (congruent dissolution; see Sect. 5.5).</p>
</sec>
<sec id="Ch1.S5.SS4">
  <label>5.4</label><title>Cave ventilation</title>
      <p id="d1e4842">The monitoring of temperature and <inline-formula><mml:math id="M291" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> between June 2017 and June 2018 shows that Waipuna Cave ventilation is driven by changes in the density of internal and external air in response to seasonal external temperature (Fig. 12), i.e. Waipuna Cave is a barometric cave sensu Fernandez-Cortes et al. (2008). This behaviour has been observed in other caves globally (Wong et al., 2011; Breitenbach et al., 2015; Riechelmann et al., 2019).</p>
      <p id="d1e4858">During late spring and summer (November 2017 to May 2018), cave air is colder than surface air (<inline-formula><mml:math id="M292" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>T</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0</mml:mn></mml:mrow></mml:math></inline-formula>) (Fig. 12c). A greater relative density of the cave air and the pressure difference compared to the surface air creates a cold-air “lake” within the cave. This cold air mass is isolated from the warmer, less dense exterior air (i.e. isolation period) due to the geometry of the cave (Fig. 14). The cold, stagnant cave air inhibits the exhalation of <inline-formula><mml:math id="M293" 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> released from the drip water, which then accumulates in the cave atmosphere. Inversely, from autumn to early spring (June 2017 to October 2017), a positive <inline-formula><mml:math id="M294" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>T</mml:mi></mml:mrow></mml:math></inline-formula> (i.e. warmer cave air relative to the surface, though still colder than summer cave air) leads to the barometric ventilation of cave air (Fig. 12c). Due to the pressure gradient, cool and dense surface air will sink into the cave, whilst rising warm cave air leaves the cave. The intensified air exchange promotes <inline-formula><mml:math id="M295" 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> extraction from the cave. This effect is reflected in the positive relation between <inline-formula><mml:math id="M296" display="inline"><mml:mrow><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">cave</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M297" 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> values (<inline-formula><mml:math id="M298" 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">0.67</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M299" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.04</mml:mn></mml:mrow></mml:math></inline-formula>).
These two phases of cave ventilation dynamics fit the chimney circulation
model (Fairchild and Baker, 2012, p. 125) and have been observed in similar
climatic settings in the USA (Oster et al., 2012), India (Breitenbach et
al., 2015), and Spain (Gázquez et al., 2017) among others.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F14"><?xmltex \currentcnt{14}?><label>Figure 14</label><caption><p id="d1e4959">Conceptual model of Waipuna Cave ventilation and cave air <inline-formula><mml:math id="M300" 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> dynamics. The cave air is warmer in summer and colder in winter.
However, in summer, the cave air is colder than surface air (<inline-formula><mml:math id="M301" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mo>+</mml:mo></mml:mrow></mml:math></inline-formula>), and in
winter, the cave air is warmer than surface air (<inline-formula><mml:math id="M302" display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mo>-</mml:mo></mml:mrow></mml:math></inline-formula>). <bold>(a)</bold> Spring and summer when warmer surface conditions compared to the cave interior leads to a stagnant cold-air lake and maximum <inline-formula><mml:math id="M303" 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> values in the cave. <bold>(b)</bold> Autumn and winter conditions characterised by low surface and relatively higher cave air temperatures, facilitating barometric ventilation and the exhalation of cave air <inline-formula><mml:math id="M304" 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> to the surface.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f14.png"/>

        </fig>

      <p id="d1e5029">Furthermore, we find that during the period with a negative <inline-formula><mml:math id="M305" display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">eff</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>,
normally the summer season, the relationship between <inline-formula><mml:math id="M306" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M307" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios is more pronounced, reflected in a higher <inline-formula><mml:math id="M308" display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> value (<inline-formula><mml:math id="M309" 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">0.92</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M310" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>) and a steeper slope compared to the winter season (<inline-formula><mml:math id="M311" 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">0.52</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M312" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.001</mml:mn></mml:mrow></mml:math></inline-formula>), when this relationship is less strong and the
slope is lower (Fig. S8). Together with lower drip water <inline-formula><mml:math id="M313" display="inline"><mml:mrow><mml:mi>X</mml:mi><mml:mo>/</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:mrow></mml:math></inline-formula> values in the winter season, this suggests a less significant role for PCP at times of higher ventilation and <inline-formula><mml:math id="M314" 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> changes in Waipuna Cave. Since all <inline-formula><mml:math id="M315" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M316" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios fall along the PCP line during the months of reduced ventilation (November–March), it seems that enhanced cave ventilation does not affect PCP.</p>
</sec>
<sec id="Ch1.S5.SS5">
  <label>5.5</label><title>Modern ENSO signature in Waipuna Cave</title>
      <p id="d1e5190">We have demonstrated that in Waipuna Cave, <inline-formula><mml:math id="M317" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M318" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios are sensitive PCP indicators. Here we discuss how they potentially react to infiltration changes governed by ENSO dynamics.</p>
      <?pagebreak page3376?><p id="d1e5217">A plot of <inline-formula><mml:math id="M319" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> versus <inline-formula><mml:math id="M320" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios displays two clusters, each along a clear trend (Figs. 10b and 15). Orange data points indicate all samples collected between October 2016 and February 2019, minus the period that comprises the blue group of samples. Blue-coloured symbols represent samples collected between February 2018 and the end of August 2018, a period with above-average rainfall, likely related to a La Niña event that developed in December 2017. These conditions prevailed over the following months (January to March 2018; NIWA, 2018a). Even though La Niña dissipated in March 2018, it still affected early-autumn circulation patterns in the central North Island, expressed generally by stronger-than-usual
northeasterly winds, average temperatures 1.2 <inline-formula><mml:math id="M321" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C higher than normal, rainfall well above normal (<inline-formula><mml:math id="M322" display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">149</mml:mn></mml:mrow></mml:math></inline-formula> % of normal), and much higher soil moisture levels for this time of year (NIWA, 2018b). Drip water samples collected before February 2018 and after August 2018 (ENSO-neutral conditions) plot on the main PCP trend, but samples collected between February and August 2018 (during a La Niña event decay) plot on a distinct line (Fig. 15). Some water samples collected on 7 February 2018 fall into the same range as the orange (stronger PCP) group, while others collected on the same day fall into the range of the blue group, potentially explaining that the cave's hydrology reacts within days to weeks (depending on drip lag response) to infiltration changes.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F15"><?xmltex \currentcnt{15}?><label>Figure 15</label><caption><p id="d1e5265">Drip water <inline-formula><mml:math id="M323" display="inline"><mml:mrow><mml:mi>ln⁡</mml:mi><mml:mo>(</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> versus <inline-formula><mml:math id="M324" display="inline"><mml:mrow><mml:mi>ln⁡</mml:mi><mml:mo>(</mml:mo><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> ratios in Waipuna Cave. Blue diamonds indicate samples collected between late February to the end of August 2018; orange circles are for all other samples collected between October 2016 and February 2019.</p></caption>
          <?xmltex \igopts{width=170.716535pt}?><graphic xlink:href="https://hess.copernicus.org/articles/24/3361/2020/hess-24-3361-2020-f15.png"/>

        </fig>

      <p id="d1e5313">It therefore seems possible to identify ENSO events by singling out
different regression trends in <inline-formula><mml:math id="M325" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M326" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> space (Fig. 15). Our data, combined with meteorological information, suggest different behaviour of <inline-formula><mml:math id="M327" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> during the warm and wet La Niña event. A comparison of intercept values of the two trend lines suggests that wet La Niña conditions promoted higher effective infiltration, thereby reducing Sr availability.</p>
      <p id="d1e5352"><inline-formula><mml:math id="M328" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M329" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios are lower during winter, the wettest months with the lowest PET. Conversely, <inline-formula><mml:math id="M330" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M331" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios are higher in the higher-PET, drier summer months (Figs. 11 and S8). We postulate that in Waipuna Cave, the La Niña climate mode, although short-lived, has a strong influence on <inline-formula><mml:math id="M332" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> variation that produces an overprint on PCP dynamics. In the case of the 2017 La Niña event, we interpret the data to indicate that the extra infiltration associated with the event fundamentally altered the regime of host rock dissolution, thereby
decreasing Sr availability (Fairchild and Treble, 2009) in a manner consistent with congruent host rock dissolution and reduced selectivity in Sr leaching (Fairchild et al., 2000). In summary, we argue that hydrological change associated with ENSO, which amplifies the length of the “wet” time window, should modulate <inline-formula><mml:math id="M333" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> to a greater extent than seasonal changes.</p>
</sec>
</sec>
<sec id="Ch1.S6" sec-type="conclusions">
  <label>6</label><title>Conclusions</title>
      <p id="d1e5435">The results of a 3-year long multi-parameter monitoring campaign in Waipuna Cave help to characterise the sensitivity of the cave with respect
to external climatic changes occurring on intra- and inter-annual timescales
in the North Island of New Zealand. The monitored parameters include drip
rates, cave air temperature, drip water trace elements, water stable
isotopes, and cave air <inline-formula><mml:math id="M334" display="inline"><mml:mrow class="chem"><mml:mi>p</mml:mi><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. These were compared to meteorological data from nearby stations. Based on geochemical and drip rate data, we identify three distinct infiltration pathways for the studied drip sites. These are type 1 – diffuse flow, type 2 – fracture flow, and type 3 – combined flow, with lagged responses to antecedent rainfall of 24–18, 4–6, and 11 d, respectively. Waipuna Cave thus reacts quickly (within less than 1 month) to external precipitation variability and is sensitive to sub-seasonal changes in epikarst hydrology.</p>
      <p id="d1e5451">Drip water isotope composition in Waipuna Cave reflects the mean rainwater
<inline-formula><mml:math id="M335" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M336" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M337" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="italic">δ</mml:mi><mml:mi mathvariant="normal">D</mml:mi></mml:mrow></mml:math></inline-formula> values. Mixing
processes in soil and epikarst obscure any seasonal isotopic signal in the
drip water. However, long-term (i.e. inter-annual to decadal) atmospheric
changes are very likely recorded by speleothem calcite <inline-formula><mml:math id="M338" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">18</mml:mn></mml:msup><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M339" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">17</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in Waipuna Cave. Because local spring and summer
rainfall isotope values are influenced by the amount effect, pronounced
droughts can affect the isotopic composition of the drip water, and that
signal may be recorded in speleothems.</p>
      <p id="d1e5518">Drip water <inline-formula><mml:math id="M340" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M341" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios are modulated by PCP and reflect local hydrological changes. Higher <inline-formula><mml:math id="M342" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M343" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios reflect periods of reduced effective infiltration from November to March when the potential evapotranspiration exceeds the local rainfall amount. The relationship between <inline-formula><mml:math id="M344" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M345" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> ratios may be affected by ENSO variability, with wetter conditions and reduced PCP occurring during La Niña events reflected in lower <inline-formula><mml:math id="M346" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Mg</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M347" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">Sr</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">Ca</mml:mi></mml:mrow></mml:math></inline-formula> slopes. This relationship may thus be a sensitive geochemical tracer of ENSO dynamics. However, longer monitoring is required to validate this interpretation.</p>
      <p id="d1e5618">Surface air temperature changes govern cave ventilation in Waipuna Cave.
Enhanced ventilation occurs between April and October (austral winter) when
the surface air temperature is lower than in the cave. During austral summer,
surface air temperatures are higher than cave air temperatures, resulting in
reduced ventilation by virtue of a cold cave air lake. The Waipuna Cave
ventilation pattern is an important factor controlling drip water degassing,
cave air <inline-formula><mml:math id="M348" 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> dynamics, speleothem growth rates, and isotope
fractionation.</p>
      <p id="d1e5633">The findings of this study on the hydrochemistry in Waipuna Cave establish a
baseline that will allow for the interpretation of speleothem-based proxy records at
seasonal and inter-annual scales to reconstruct local hydrological changes as
well as regional dynamics, e.g. ENSO events. Longer-term monitoring is
required in order to better constrain the effects of synoptic-scale
environmental fluctuations on speleothem records from Waipuna Cave and
nearby caves.</p>
</sec>

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

      <p id="d1e5640">Data reported here are available to the public as data tables in the Supplement. Additionally, data can be requested from the corresponding author (Cinthya Nava-Fernandez, cinthya.navafernandez@rub.de).</p>
  </notes><?xmltex \hack{\newpage}?><app-group>
        <supplementary-material position="anchor"><p id="d1e5644">The supplement related to this article is available online at: <inline-supplementary-material xlink:href="https://doi.org/10.5194/hess-24-3361-2020-supplement" xlink:title="zip">https://doi.org/10.5194/hess-24-3361-2020-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e5653">CNF conducted fieldwork, collected the samples and data, analysed the data, and prepared the original draft of the paper. AH designed and carried out the cave-monitoring programme, conducted fieldwork, and supervised the study. FG conducted the stable water analyses and contributed to the discussion of the results. OK participated in the fieldwork, contributed to the discussion, helped with the figures, supervised the study, and contributed to the discussion. NM helped with the statistical analysis and discussion. BF conducted fieldwork and helped with the statistical analysis and writing. JH performed fieldwork and contributed the structure-from-motion images. AP and BW helped in the cave-monitoring effort. AF carried out the major and trace elements analysis and contributed to the discussion. DAH provided laboratory resources and helped in the acquisition of funding. AI contributed to the editing process. SFMB designed the monitoring programme, supervised the study, collected samples, and contributed to the interpretation, visualisation, and preparation of the paper.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e5659">The authors declare that they have no conflict of interest.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e5665">Thanks go to Ingrid Lindeman, Inken Heidke, and Jackson White for their valuable
fieldwork contributions. We thank Peter and Libby Chandler for their
permission to access Waipuna Cave and their ongoing support of research.
Cinthya Nava-Fernandez acknowledges financial support from the German Academic Exchange Service (DAAD). Fernando Gázquez was financially supported by the HIPATIA research programme of the University of Almería.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e5670">This research has been supported by the European Union's Horizon 2020 Research and Innovation programme through a Marie Skłodowska-Curie grant (no. 691037), the Royal Society of New Zealand (grant no. RIS-UOW1501), and the Rutherford Discovery Fellowship programme (grant no. RDF-UOW1601). <?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> This open-access publication was funded <?xmltex \hack{\newline}?> by Ruhr-Universität Bochum.</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e5682">This paper was edited by Gerrit H. de Rooij and reviewed by two anonymous referees.</p>
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    <!--<article-title-html>Pacific climate reflected in Waipuna Cave  drip water hydrochemistry</article-title-html>
<abstract-html><p>Cave microclimate and geochemical monitoring is vitally important for
correct interpretations of proxy time series from speleothems with regard to past climatic and environmental dynamics. We present results of a
comprehensive cave-monitoring programme in Waipuna Cave in the North Island
of New Zealand, a region that is strongly influenced by the Southern
Westerlies and the El Niño–Southern Oscillation (ENSO). This study aims to characterise the response of the Waipuna Cave hydrological system to atmospheric circulation dynamics in the southwestern Pacific region in order to assure the quality of ongoing palaeo-environmental reconstructions from this cave.</p><p>Drip water from 10 drip sites was collected at roughly monthly intervals for
a period of ca. 3 years for isotopic (<i>δ</i><sup>18</sup>O, <i>δ</i>D, d-excess parameter, <i>δ</i><sup>17</sup>O, and <sup>17</sup>O<sub>excess</sub>) and elemental (Mg∕Ca and Sr∕Ca) analysis. The monitoring included spot measurements of drip rates and cave air CO<sub>2</sub> concentration. Cave air temperature and drip rates were also continuously recorded by automatic loggers. These datasets were compared to surface air temperature, rainfall, and potential evaporation from nearby meteorological stations to test the degree of signal transfer and expression of surface environmental conditions in Waipuna Cave hydrochemistry.</p><p>Based on the drip response dynamics to rainfall and other characteristics, we
identified three types of discharge associated with hydrological routing in
Waipuna Cave: (i) type 1 – diffuse flow, (ii) type 2 – fracture flow, and (iii) type 3 – combined flow. Drip water isotopes do not reflect seasonal
variability but show higher values during severe drought. Drip water <i>δ</i><sup>18</sup>O values are characterised by small variability and reflect the mean isotopic signature of precipitation, testifying to rapid and thorough homogenisation in the epikarst. Mg∕Ca and Sr∕Ca ratios in drip waters are predominantly controlled by prior calcite precipitation (PCP). Prior calcite precipitation is strongest during austral summer (December–February), reflecting drier conditions and a lack of effective infiltration, and is weakest during the wet austral winter (July–September). The Sr∕Ca ratio is particularly sensitive to ENSO conditions due to the interplay of congruent or incongruent host rock dissolution, which manifests itself in lower Sr∕Ca in above-average warmer and wetter (La Niña-like) conditions. Our
microclimatic observations at Waipuna Cave provide a valuable baseline for the
rigorous interpretation of speleothem proxy records aiming at reconstructing
the past expression of Pacific climate modes.</p></abstract-html>
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