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  <front>
    <journal-meta><journal-id journal-id-type="publisher">BG</journal-id><journal-title-group>
    <journal-title>Biogeosciences</journal-title>
    <abbrev-journal-title abbrev-type="publisher">BG</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Biogeosciences</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1726-4189</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/bg-14-5471-2017</article-id><title-group><article-title>Capturing temporal and spatial variability in the chemistry of shallow
permafrost ponds</article-title>
      </title-group><?xmltex \runningtitle{Capturing temporal and spatial variability}?><?xmltex \runningauthor{M.~Q. Morison et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Morison</surname><given-names>Matthew Q.</given-names></name>
          <email>mmorison@uwaterloo.ca</email>
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Macrae</surname><given-names>Merrin L.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Petrone</surname><given-names>Richard M.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Fishback</surname><given-names>LeeAnn</given-names></name>
          
        </contrib>
        <aff id="aff1"><label>1</label><institution>Department of Geography and Environmental Management, University of
Waterloo, Waterloo, N2L 3G1, Canada</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Churchill Northern Studies Centre, Churchill, R0B 0E0, Canada</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Matthew Q. Morison (mmorison@uwaterloo.ca)</corresp></author-notes><pub-date><day>4</day><month>December</month><year>2017</year></pub-date>
      
      <volume>14</volume>
      <issue>23</issue>
      <fpage>5471</fpage><lpage>5485</lpage>
      <history>
        <date date-type="received"><day>15</day><month>April</month><year>2017</year></date>
           <date date-type="rev-request"><day>11</day><month>May</month><year>2017</year></date>
           <date date-type="rev-recd"><day>25</day><month>October</month><year>2017</year></date>
           <date date-type="accepted"><day>3</day><month>November</month><year>2017</year></date>
      </history>
      <permissions>
        
        
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/3.0/">https://creativecommons.org/licenses/by/3.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017.html">This article is available from https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017.html</self-uri><self-uri xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017.pdf">The full text article is available as a PDF file from https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017.pdf</self-uri>
      <abstract>
    <p id="d1e111">Across the circumpolar north, the fate of small freshwater ponds and lakes
(<inline-formula><mml:math id="M1" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 1 km<inline-formula><mml:math id="M2" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> has been the subject of scientific interest due to their
ubiquity in the landscape, capacity to exchange carbon and energy with the
atmosphere, and their potential to inform researchers about past climates
through sediment records. A changing climate has implications for the
capacity of ponds and lakes to support organisms and store carbon, which in
turn has important feedbacks to climate change. Thus, an improved
understanding of pond biogeochemistry is needed. To characterize spatial and
temporal patterns in water column chemistry, a suite of tundra ponds were
examined to answer the following research questions:
(1) does temporal variability exceed spatial variability? (2) If temporal
variability exists, do all ponds (or groups of ponds) behave in a similar
temporal pattern, linked to seasonal hydrologic drivers or precipitation
events? Six shallow ponds located in the Hudson Bay Lowlands region were
monitored between May and October 2015 (inclusive, spanning the entire
open-water period). The ponds span a range of biophysical conditions
including pond area, perimeter, depth, and shoreline development. Water
samples were collected regularly, both bimonthly over the ice-free season and
intensively during and following a large summer storm event. Samples were
analysed for nitrogen speciation (NO<inline-formula><mml:math id="M3" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, NH<inline-formula><mml:math id="M4" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, dissolved
organic nitrogen) and major ions (Cl<inline-formula><mml:math id="M5" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M6" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, K<inline-formula><mml:math id="M7" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>,
Ca<inline-formula><mml:math id="M8" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, Mg<inline-formula><mml:math id="M9" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M10" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. Across all ponds, temporal variability
(across the season and within a single rain event) exceeded spatial
variability (variation among ponds) in concentrations of several major
species (Cl<inline-formula><mml:math id="M11" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M12" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, K<inline-formula><mml:math id="M13" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Ca<inline-formula><mml:math id="M14" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M15" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>.
Evapoconcentration and dilution of pond water with precipitation and runoff
inputs were the dominant processes influencing a set of chemical species
which are hydrologically driven (Cl<inline-formula><mml:math id="M16" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M17" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M18" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Mg<inline-formula><mml:math id="M19" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>,
dissolved organic nitrogen), whereas the dissolved inorganic nitrogen species
were likely mediated by processes within ponds. This work demonstrates the
importance of understanding hydrologically driven chemodynamics in permafrost
ponds on multiple scales (seasonal and event scale).</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p id="d1e332">Small, shallow freshwater bodies (<inline-formula><mml:math id="M20" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 1 km<inline-formula><mml:math id="M21" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> across the circumpolar
north are ubiquitous in the landscape (Muster et al., 2013; Dyke and Sladen,
2010; Macrae et al., 2014). In many regions, these features maintain the
capacity to store and exchange carbon (C) (Macrae et al., 2004; Abnizova et
al., 2012), act as a habitat (Smol and Douglas, 2007), and mediate the
landscape energy balance (Chapin et al., 2000). These tundra ponds are highly
sensitive to climate change (Schindler and Smol, 2006), which may impact
their hydrology and biogeochemistry. This has implications for their ability
to support organisms and store or cycle C, which in turn has important
feedbacks to climate change. Thus, an improved understanding of pond
biogeochemistry is needed. Climate change may impact pond hydrobiogeochemical
conditions by modifying pond hydrologic and thermal conditions, as well as
pond–catchment connectivity. In permafrost systems, recent work has focused
on the impact of climatically induced permafrost thaw on lake and pond
chemistry (Vonk et al., 2015) over a timescale of decades, generally showing
increasing concentrations of ions indicative of deeper flow paths and
weathering processes (Kokelj et al., 2009). Lougheed et al. (2011) examined
changes in tundra pond chemistry over 40 years in Alaska and observed
substantial increases in inorganic nutrients, which were attributed to a
thaw-based release from shallow permafrost and increased atmospheric nitrogen
(N) deposition. In addition to changing chemical contributions from thawing
catchments, the water balances of ponds are sensitive to climatic changes
that impact the ponds directly as well as indirectly through changing
catchment hydromorphology (Walvoord and Kurylyk, 2016). Adjacent to pond
edges, thermokarst expansion acts as a mechanism for lateral seepage and loss
(e.g. Yoshikawa and Hinzman, 2003) leading to increased connectivity,
potentially modifying seasonal biogeochemical trajectories (Abbott et al.,
2015). Elevated levels of nutrients and/or ions may impact the C uptake
function of ponds via primary productivity, which has been shown to be
nutrient-limited in subarctic and Arctic freshwater bodies (Levine and
Whalen, 2001; Bergström et al., 2005; Bergström, 2010; Bonilla et
al., 2005; Symons et al., 2012). Indeed, increased nutrient loading to ponds
may either bring about an increase in pond primary productivity (Levine and
Whalen, 2001; O'Brien et al., 2005) or may lead to a decrease through
increased turbidity and suboptimal conditions for photosynthesis (northern
Sweden: Ask et al., 2009; northern Québec: Roiha et al., 2015), linking
nutrient concentrations to biological markers such as chlorophyll (Przytulska
et al., 2016).</p>
      <p id="d1e354">Although climate change may lead to long-term changes in pond permanence and
hydrologic exchange, pond hydrologic storage can also vary greatly over the
course of a single season or among different hydrologic years (Morison et
al., 2017; Woo and Guan, 2006). Annual changes to pond storage often reflect
the highly variable local climatic conditions, and ponds may either desiccate
completely (e.g. Bouchard et al., 2013; Smith et al., 2005) or spill over
bankfull storage and/or coalesce (Macrae et al., 2014). The chemical
concentrations of the water column in ponds is closely tied to hydrology,
both directly through physical processes (i.e. dilution and
evapoconcentration; Borghini et al., 2013) and indirectly through mediating
environmental factors that control the rate of biogeochemical processes (e.g.
variable pond depth controlling the diurnal water temperature amplitude; Smol
and Douglas, 2007). Mazurek et al. (2012) sampled shallow ponds over several
summer seasons in Svalbard and found ionic concentrations increasing in ponds
over the summer months, coincident with pond drying. White et al. (2014)
monitored ponds at three time steps over the ice-free season and related pond
seasonal biogeochemical trajectories to pond morphology and pond–peatland
connectivity. Given the significant control of hydrological processes on pond
biogeochemistry, and the highly variable hydrological conditions experienced
by ponds within a single season, an improved understanding of seasonal
patterns of pond hydrochemistry is needed to better understand potential pond
responses to climate change.</p>
      <p id="d1e357">The concepts of hydrochemical coherence (or synchrony; Baines et al., 2000)
have been employed in temperate lake systems to determine the role of
different climatic and hydrological factors in driving lake chemical
variations, often by examining correlation of different chemical measures
across space (e.g. Magnuson et al., 1990). For instance, Pace and Cole (2002)
found in northern Michigan that changes to dissolved organic carbon
and colour were synchronous among lakes while total phosphorus, chlorophyll,
and pH were not. Other methods, such as the use of evaporative normalization
factors (e.g. Borghini et al., 2013), have allowed for comparisons among
difference chemical species and the degree to which they are driven by
hydrological variation. Both of these methods allow for comparison of
relative deviations of values which would otherwise be masked by absolute
differences among lakes. Approaches of hydrochemical coherence have been
less seldom employed in subarctic permafrost pond and lake settings.</p>
      <p id="d1e360">Recent approaches to characterizing shallow pond biogeochemical processes
across Arctic, Antarctic, and alpine permafrost settings have used three to
four water samples from each lake or pond, taken at different points of the
ice-free season to represent “early-season”, “mid-season”, and
“late-season” conditions. Other approaches have relied on a single annual
sample to characterize various geochemical indicators of ponds, such as
nutrient status, carbon dynamics, and major ion and metal concentrations, often
sampling many ponds and lakes (often 10–100) during that single time period
(Table S1 in the Supplement). However, given the variability in pond storage and
hydrological conditions over the course of an ice-free season, it is
important to frame the results of pond chemical analyses in the proper
hydrologic context and, further, to be prudent in generalizing pond
geochemical process from samples taken in different hydrological periods.
Beyond broad spatial sampling campaigns of many periods at a coarse temporal
resolution, less is known about the amplitude, drivers, and total variation
in seasonal and event chemographs of shallow ponds in remote northern
catchments, despite their importance in driving key ecological functions
across the circumpolar north. Further, as large summer storms increase in
frequency and magnitude (Sauchyn and Kulshreshtha, 2008; Kaufman et al.,
2009), it is important to understand how storm events control short-term
water chemistry variation, which can represent a substantial proportion of
the annual water balance over a period of hours to days (Macrae et al.,
2014).</p>
      <p id="d1e364">The objectives of this study were to characterize spatial and temporal
patterns in the chemistry of a suite of tundra ponds to determine if
(1) temporal variability exceeded spatial variability throughout the
open-water season; (2) temporal variability existed, whether all ponds (or
groups of ponds) behaved in a similar temporal pattern, linked to season or
hydrology; and (3) spatiotemporal variability in pond biogeochemical
signatures could be used to make inferences about processes occurring within
ponds and between ponds and surrounding peatlands. This information will
improve our understanding of hydrobiogeochemical processes in tundra ponds,
particularly in terms of seasonal patterns, and will aid in developing
appropriate sampling designs in future. Further, this study provides a
geochemical survey of six ponds in the Hudson Bay Lowlands region on two
unprecedented temporal scales (bimonthly), spanning an ice-free season, in
addition to diurnal samples spanning an intense rainfall-runoff event.</p>
</sec>
<sec id="Ch1.S2">
  <title>Methods</title>
<sec id="Ch1.S2.SS1">
  <title>Study site and sampling design</title>
      <p id="d1e378">This study was completed in the Hudson Bay Lowlands (HBL), approximately
20 km east of the town of Churchill, Manitoba, Canada. The regional climate
is strongly influenced by the close proximity to Hudson Bay (Rouse, 1991),
with average air temperatures in the region (1980–2010 normal) of
<inline-formula><mml:math id="M22" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6.5</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M23" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C (annually) with a snow-free season from May to October,
and maximum temperatures in July (monthly average 12.7 <inline-formula><mml:math id="M24" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C;
Government of Canada, 2016).</p>
      <p id="d1e409">The HBL are the largest contiguous wetland complex in North America, with
thousands of lakes and ponds in the landscape (Keller et al., 2014; Dyke and
Sladen, 2010) from impeded drainage due very low topographic gradients
(Boudreau and Rouse, 1995) and the presence of permafrost. Ponds have been
demonstrated to be stably stratified in the eastern HBL (Deshpande et al.,
2015), while the very shallow (<inline-formula><mml:math id="M25" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 1 m) ponds in the western HBL are
assumed to be well mixed by wind action (Bello and Smith, 1990). Ponds in
the western HBL have been shown to be nutrient-limited (Eichel et al., 2014;
Symons et al., 2012), restricted in surface and groundwater connection
(Boudreau and Rouse, 1995), with steep banks and thick, organic sediments
with dense mats of benthic blue-green, green, and diatomaceous algae (Macrae
et al., 2004; Gray, 1987), with the dominant diatom genus being <italic>Denticula</italic> (Macrae et
al., 2004). Symons et al. (2012) showed the most abundant phytoplankton
communities to be <italic>Chlamydomonas</italic> spp., <italic>Sphaerocystis</italic> spp.,
<italic>Diatoma</italic> spp., and <italic>Crugienella</italic> spp. Due to their small size and
extremely alkaline conditions (8 to 9.8 pH; Macrae et al., 2004; Bos and
Pellatt, 2012), ponds are devoid of fish communities with the exception of
stickleback (<italic>Gasterosteidae</italic>). Ponds are also devoid of aquatic macrophytes with the
exception of <italic>Carex aquatilis</italic> found along pond perimeters in zones where water is shallow.
Eichel et al. (2014) demonstrated the importance of benthic organisms to the
cycling of nutrients in these ponds, showing experimentally that mesocosms
with sediment removed inorganic nutrients from the water column at a rate
orders of magnitude greater than mesocosms without sediment.</p>
      <p id="d1e441">The ponds and their catchments are underlain by continuous permafrost, with a
seasonal active layer of 40–100 cm thickness. In the catchments, there is a
peat layer of 30–60 cm overlying unsorted glaciomarine till. The surface is
comprised of patterned polygonal peat plateaus segregated by sedge lawn and
narrow fen channel networks. Dry uplands (plateau) are dominated by
lichen–heath communities, with sparse tree cover (<italic>Larix</italic> spp. and
<italic>Salix</italic> spp.). Transition zones (moderate moisture, sedge lawns) are
comprised of hummocks and hollows, dominated by a mixture of lichen–heath
communities and <italic>Carex mitis</italic>. Low-lying channel fens (saturated) are
dominated by <italic>Carex aquatilis</italic>. Dwarf shrubs (<italic>Betula glandulosa</italic> and <italic>Salix arctica</italic>) are also found in some channel fens
and around pond perimeters.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><caption><p id="d1e465">Site map of the general near-coastal tundra region with the
catchment areas containing Frisbee, Larch, Strange, Sandwich, Left, and Erin
ponds. Inset map highlights the entire Hudson Bay Lowlands (dark coloured
region to the south of Hudson Bay) and the Churchill study region (indicated
with a red dot and an arrow). Map data: Google, Digital Globe, 2017.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f01.pdf"/>

        </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p id="d1e478">Physical characteristics and locations of study ponds near
Churchill, Manitoba.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="7">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="left"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Pond</oasis:entry>  
         <oasis:entry colname="col2">Area</oasis:entry>  
         <oasis:entry colname="col3">Perimeter</oasis:entry>  
         <oasis:entry colname="col4">Shoreline</oasis:entry>  
         <oasis:entry colname="col5">Average depth,</oasis:entry>  
         <oasis:entry colname="col6">Catchment area</oasis:entry>  
         <oasis:entry colname="col7"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">(m<inline-formula><mml:math id="M31" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">(m)</oasis:entry>  
         <oasis:entry colname="col4">development<inline-formula><mml:math id="M32" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M33" display="inline"><mml:mrow><mml:mi mathvariant="italic">μ</mml:mi><mml:mo>±</mml:mo><mml:mi mathvariant="italic">σ</mml:mi></mml:mrow></mml:math></inline-formula> (cm)</oasis:entry>  
         <oasis:entry colname="col6">(m<inline-formula><mml:math id="M34" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">Coordinates</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4">(m<inline-formula><mml:math id="M35" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">1</mml:mn></mml:msup></mml:math></inline-formula> m<inline-formula><mml:math id="M36" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Erin</oasis:entry>  
         <oasis:entry colname="col2">8479</oasis:entry>  
         <oasis:entry colname="col3">448</oasis:entry>  
         <oasis:entry colname="col4">1.37</oasis:entry>  
         <oasis:entry colname="col5">No data</oasis:entry>  
         <oasis:entry colname="col6">108 160</oasis:entry>  
         <oasis:entry colname="col7">58<inline-formula><mml:math id="M37" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>43<inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>14.3<inline-formula><mml:math id="M39" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> N, 93<inline-formula><mml:math id="M40" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>50<inline-formula><mml:math id="M41" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>20.2<inline-formula><mml:math id="M42" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> W</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Left</oasis:entry>  
         <oasis:entry colname="col2">752</oasis:entry>  
         <oasis:entry colname="col3">130</oasis:entry>  
         <oasis:entry colname="col4">1.34</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M43" display="inline"><mml:mrow><mml:mn mathvariant="normal">30.0</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">6.8</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">5737</oasis:entry>  
         <oasis:entry colname="col7">58<inline-formula><mml:math id="M44" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>44<inline-formula><mml:math id="M45" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>44.2<inline-formula><mml:math id="M46" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> N, 93<inline-formula><mml:math id="M47" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>49<inline-formula><mml:math id="M48" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>20.6<inline-formula><mml:math id="M49" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> W</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Strange</oasis:entry>  
         <oasis:entry colname="col2">6307</oasis:entry>  
         <oasis:entry colname="col3">424</oasis:entry>  
         <oasis:entry colname="col4">1.51</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M50" display="inline"><mml:mrow><mml:mn mathvariant="normal">22.2</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">10.0</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">20 441</oasis:entry>  
         <oasis:entry colname="col7">58<inline-formula><mml:math id="M51" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>43<inline-formula><mml:math id="M52" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>36.8<inline-formula><mml:math id="M53" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> N, 93<inline-formula><mml:math id="M54" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>50<inline-formula><mml:math id="M55" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>20.6<inline-formula><mml:math id="M56" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> W</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Sandwich</oasis:entry>  
         <oasis:entry colname="col2">17 146</oasis:entry>  
         <oasis:entry colname="col3">548</oasis:entry>  
         <oasis:entry colname="col4">1.18</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M57" display="inline"><mml:mrow><mml:mn mathvariant="normal">19.6</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">4.8</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">34 638</oasis:entry>  
         <oasis:entry colname="col7">58<inline-formula><mml:math id="M58" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>43<inline-formula><mml:math id="M59" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>24.2<inline-formula><mml:math id="M60" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> N, 93<inline-formula><mml:math id="M61" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>50<inline-formula><mml:math id="M62" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>34.4<inline-formula><mml:math id="M63" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> W</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Frisbee</oasis:entry>  
         <oasis:entry colname="col2">4416</oasis:entry>  
         <oasis:entry colname="col3">258</oasis:entry>  
         <oasis:entry colname="col4">1.10</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M64" display="inline"><mml:mrow><mml:mn mathvariant="normal">14.2</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">2.8</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">31 128</oasis:entry>  
         <oasis:entry colname="col7">58<inline-formula><mml:math id="M65" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>43<inline-formula><mml:math id="M66" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>35.5<inline-formula><mml:math id="M67" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> N, 93<inline-formula><mml:math id="M68" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>50<inline-formula><mml:math id="M69" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>33.9<inline-formula><mml:math id="M70" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> W</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Larch</oasis:entry>  
         <oasis:entry colname="col2">4066</oasis:entry>  
         <oasis:entry colname="col3">333</oasis:entry>  
         <oasis:entry colname="col4">1.47</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M71" display="inline"><mml:mrow><mml:mn mathvariant="normal">14.2</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">4.9</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">15 228</oasis:entry>  
         <oasis:entry colname="col7">58<inline-formula><mml:math id="M72" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>43<inline-formula><mml:math id="M73" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>26.9<inline-formula><mml:math id="M74" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> N, 93<inline-formula><mml:math id="M75" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>50<inline-formula><mml:math id="M76" display="inline"><mml:msup><mml:mi/><mml:mo>′</mml:mo></mml:msup></mml:math></inline-formula>41.5<inline-formula><mml:math id="M77" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>′</mml:mo><mml:mo>′</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> W</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e481"><inline-formula><mml:math id="M26" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula> Shoreline development, <inline-formula><mml:math id="M27" display="inline"><mml:mrow><mml:msub><mml:mi>D</mml:mi><mml:mtext>L</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, is the ratio of
measured shoreline perimeter, <inline-formula><mml:math id="M28" display="inline"><mml:mi>P</mml:mi></mml:math></inline-formula>, of a given pond to the shoreline perimeter
of a perfectly circular pond of equal area, <inline-formula><mml:math id="M29" display="inline"><mml:mi>A</mml:mi></mml:math></inline-formula>, such that
<inline-formula><mml:math id="M30" display="inline"><mml:mrow><mml:msub><mml:mi>D</mml:mi><mml:mtext>L</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mi>P</mml:mi><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:msqrt><mml:mrow><mml:mi mathvariant="italic">π</mml:mi><mml:mi>A</mml:mi></mml:mrow></mml:msqrt></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:math></inline-formula> (Aronow, 1982).</p></table-wrap-foot></table-wrap>

      <p id="d1e1267">Six study ponds were selected: Erin pond, Frisbee pond, Larch pond, Left
pond, Strange pond, and Sandwich pond (Fig. 1). These ponds were selected for
their range in surface areas, perimeter, catchment area, and depth because
they have been the subject of long-term research in the area and have been
shown to be representative of a range of chemical and hydrological properties
(Table 1; Macrae et al., 2004; White et al., 2014; Wolfe et al., 2011; Bos
and Pellatt, 2012). Each pond was sampled regularly (every 14 days)
throughout the ice-free season of 2015, from day of year (DOY) 140 to 300
(May to October). Additionally, during an intensive storm during
DOY 185–188, ponds were sampled twice per day during the storm and 24 h
following the event to determine the hydrochemical impacts of a storm event,
including the inputs of both direct precipitation and runoff water. Pond
stage (water column depth) data were recorded hourly with pressure
transducers (HOBO U20, Onset Ltd.) installed in PVC (50 mm inner diameter)
slotted pipes located within 1 m of the shore of each pond (with the
exception of Erin pond) and corrected with a barometric logger housed in an
identical PVC pipe to minimize temperature-related artifacts in pressure
differences between barometric and level loggers (McLaughlin and Cohen,
2011). Precipitation data were taken from the Environment Canada
“Churchill” station (20 km west of the study site). Runoff was determined
as the residual change in pond storage exceeding the input from direct
precipitation during and up to 24 h. following a rain event, after Morison
et al. (2017). The perimeter and area of each pond were surveyed with a
Trimble Juno SB GPS unit, with a differentially corrected horizontal accuracy
of <inline-formula><mml:math id="M78" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>5 m.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Water chemistry sampling and analysis</title>
      <p id="d1e1283">Samples of pond water were collected manually as a depth-integrated profile
of the water column, approximately 3 m from the pond edge, and placed in
sterile, triple-primed 50 mL polyethylene containers. Care was taken to not
disturb pond sediments when samples were being collected. Samples were
preserved on ice in the field and passed through a 0.45 <inline-formula><mml:math id="M79" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>m
cellulose acetate filter within 2 h of collection. A 50 mL subsample was
acidified to a final concentration of 0.2 % H<inline-formula><mml:math id="M80" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>SO<inline-formula><mml:math id="M81" display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> and stored
until digestion. Non-acidified samples were immediately frozen. All samples
were shipped to the Biogeochemistry Lab at the University of Waterloo for
analysis. In the lab, acidified samples were digested (Kjeldahl digestions,
Seal Analytical Hot Block Digestion System BD50, Seattle, USA) for the
analysis of dissolved Kjeldahl N (DKN). Digested samples and non-acidified
subsamples were analysed for N species using colorimetric methods:
(Bran+Luebbe AutoAnalyzer III, Seal Analytical: methods G-102-93, (ammonium;
NH<inline-formula><mml:math id="M82" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N); G-103-93 (SRP-P), G-109-94 (nitrate; NO<inline-formula><mml:math id="M83" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>-N),
G-189-97 (DKN)). Results for NH<inline-formula><mml:math id="M84" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and NO<inline-formula><mml:math id="M85" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> have a detection
limit of 0.001 mg N L<inline-formula><mml:math id="M86" 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>. Dissolved organic nitrogen (DON)
concentrations were determined as the difference between DKN and NH<inline-formula><mml:math id="M87" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>
concentrations. Samples were analysed for other major ions: chloride
(Cl<inline-formula><mml:math id="M88" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, sulfate (SO<inline-formula><mml:math id="M89" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, sodium (Na<inline-formula><mml:math id="M90" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, potassium (K<inline-formula><mml:math id="M91" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>,
magnesium (Mg<inline-formula><mml:math id="M92" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, and calcium (Ca<inline-formula><mml:math id="M93" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> using ion chromatography
(DIONEX ICS 3000, IonPac AS18 and CS16 analytical columns).</p>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Statistical techniques</title>
      <p id="d1e1474">Due to large variability (spatial and temporal) in absolute values of
concentration across the dataset, values were normalized as deviations from
mean values to permit their comparison (Schönfeld and Numberger, 2007;
Viner, 1984). This was accomplished by examining the departure of each
sampling point from the mean of either temporal or spatial groups. More
specifically, for each measurement, proportional deviations from either
spatial or temporal means were determined as the absolute difference from
unity of either the
ratio of the measured sample concentration at a particular date and pond
(<inline-formula><mml:math id="M94" display="inline"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>st</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>) to the mean concentration of the species from all ponds
sampled that date (<inline-formula><mml:math id="M95" display="inline"><mml:mover accent="true"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>t</mml:mtext></mml:msub></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:math></inline-formula>) to examine spatial deviations
(Eq. 1) or the ratio of the measured sample concentration to the mean
concentration of the species from all samples taken from that pond over the
entire study period (<inline-formula><mml:math id="M96" display="inline"><mml:mover accent="true"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>s</mml:mtext></mml:msub></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:math></inline-formula>) to examine temporal
deviations (Eq. 2).

                <disp-formula specific-use="align" content-type="numbered"><mml:math id="M97" display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E1"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mfenced close="|" open="|"><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>st</mml:mtext></mml:msub></mml:mrow><mml:mover accent="true"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>t</mml:mtext></mml:msub></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:mfrac></mml:mstyle><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mfenced><mml:mo>=</mml:mo><mml:mtext>spatial deviation score</mml:mtext></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E2"><mml:mtd/><mml:mtd><mml:mstyle class="stylechange" displaystyle="true"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:mfenced close="|" open="|"><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>st</mml:mtext></mml:msub></mml:mrow><mml:mover accent="true"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>s</mml:mtext></mml:msub></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:mfrac></mml:mstyle><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mfenced><mml:mo>=</mml:mo><mml:mtext>temporal deviation score</mml:mtext></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula></p>
      <p id="d1e1615">Thus, each sample (<inline-formula><mml:math id="M98" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">72</mml:mn></mml:mrow></mml:math></inline-formula>; 12 samples from each of six ponds) is associated
with both a temporal deviation score and spatial deviation score for each
chemical species. Once a set of deviation scores was computed for each
species, a Mann–Whitney test was used to determine if there was a
significant difference between the medians of the set of spatial deviation
scores and the set of temporal deviation scores for each chemical species.</p>
      <p id="d1e1630">To determine the relationship between pond volume and concentrations of
different chemical species, a power function (Eq. 3) was fit to the spatially
normalized concentration (the ratio of each concentration to the mean
concentration <inline-formula><mml:math id="M99" display="inline"><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mtext>t</mml:mtext></mml:msub></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and stage data to represent the
geometry of conical bathymetry (based on observations and measurements of
several sediment basins) in the nonlinear pond stage–volume relationship.
            <disp-formula id="Ch1.E3" content-type="numbered"><mml:math id="M100" display="block"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:mo>]</mml:mo><mml:mo>=</mml:mo><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>(</mml:mo><mml:mi mathvariant="normal">stage</mml:mi><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:msup></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e1686">The parameter <inline-formula><mml:math id="M101" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is invariant under linear translation, such as
spatial normalization, and is expected to maintain a negative value with the
magnitude depending on the bathymetry of the pond (with a theoretical value
of 0 for a cylindrical flat-bottomed pond, and highly negative for a steep
conically shaped pond basin). The fit of each power function was assessed for
each chemical species in each pond with the root-mean-square error (RMSE), as the
coefficient of determination <inline-formula><mml:math id="M102" 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> is inappropriate for the nonlinear case
(Spiess and Neumeyer, 2010). Since the pond mean-normalized concentrations
are dimensionless and not scale-dependant, the RMSE term is
also dimensionless and can be compared across ponds and chemical species. The
degree of hydrologic control on different nutrient species concentrations was
manually determined by the goodness of fit of a power curve to each set of
normalized concentration data against pond stage for each of the five
instrumented ponds. In each pond, chemical species with a constant
pond-specific value of <inline-formula><mml:math id="M103" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (the slope of the power curve) with low RMSE were categorized as hydrologically driven,
where species with either (1) a <inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> value inconsistent with other
hydrologically driven species or (2) poor performance (greater RMSE) were categorized as non-hydrologically driven.</p>
      <p id="d1e1734">A principal component analysis (PCA; Dunteman, 1994) was employed on
logarithmically transformed hydrochemistry data, using singular value
decomposition scaled to have unit variance. PCA has been used before in
explorations of pond chemical trajectories over a scale of months to years
(White et al., 2014; Sokal et al., 2010; Wiklund et al.,
2012).<?xmltex \hack{\newpage}?></p>
      <p id="d1e1738">Coherence was assessed by Pearson correlation following the approach of
Magnuson et al. (1990), both among lakes for each chemical species as well
as for each chemical species (in all lakes combined). All statistical
analyses were conducted with R software (version 3.3.2, R Development Core
Team, 2016).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><caption><p id="d1e1743">Boxplots of spatial and temporal proportional deviations for each
chemical species. Significant differences between medians (<inline-formula><mml:math id="M105" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.01</mml:mn></mml:mrow></mml:math></inline-formula>) are
present for all species on the left side of the panel (Cl<inline-formula><mml:math id="M106" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>,
SO<inline-formula><mml:math id="M107" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, Na<inline-formula><mml:math id="M108" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M109" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Ca<inline-formula><mml:math id="M110" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, and no significant difference
is present for species on the right (DON, Mg<inline-formula><mml:math id="M111" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, NH<inline-formula><mml:math id="M112" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>,
NO<inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f02.pdf"/>

        </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><caption><p id="d1e1863">Correlation coefficients among ponds for all species. Values are
bolded when the correlation is significant at the <inline-formula><mml:math id="M114" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.01</mml:mn></mml:mrow></mml:math></inline-formula>
level.</p></caption><oasis:table frame="topbot"><?xmltex \begin{scaleboxenv}{.92}[.92]?><oasis:tgroup cols="12">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right" colsep="1"/>
     <oasis:colspec colnum="7" colname="col7" align="left"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:colspec colnum="11" colname="col11" align="right"/>
     <oasis:colspec colnum="12" colname="col12" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Species/pond</oasis:entry>  
         <oasis:entry colname="col2">Erin</oasis:entry>  
         <oasis:entry colname="col3">Frisbee</oasis:entry>  
         <oasis:entry colname="col4">Larch</oasis:entry>  
         <oasis:entry colname="col5">Left</oasis:entry>  
         <oasis:entry colname="col6">Sandwich</oasis:entry>  
         <oasis:entry colname="col7">Species/pond</oasis:entry>  
         <oasis:entry colname="col8">Erin</oasis:entry>  
         <oasis:entry colname="col9">Frisbee</oasis:entry>  
         <oasis:entry colname="col10">Larch</oasis:entry>  
         <oasis:entry colname="col11">Left</oasis:entry>  
         <oasis:entry colname="col12">Sandwich</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">DON</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Mg<inline-formula><mml:math id="M115" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Frisbee</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.761</bold></oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6">Frisbee</oasis:entry>  
         <oasis:entry colname="col7"><bold>0.935</bold></oasis:entry>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Larch</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.802</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.687</bold></oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Larch</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.830</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.881</bold></oasis:entry>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Left</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.794</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.912</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.846</bold></oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Left</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.912</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.944</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.878</bold></oasis:entry>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Sandwich</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.860</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.689</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.965</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.829</bold></oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Sandwich</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.904</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.905</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.946</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.952</bold></oasis:entry>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Strange</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.763</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.904</bold></oasis:entry>  
         <oasis:entry colname="col4">0.659</oasis:entry>  
         <oasis:entry colname="col5"><bold>0.900</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.688</bold></oasis:entry>  
         <oasis:entry colname="col7">Strange</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.929</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.905</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.831</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.979</bold></oasis:entry>  
         <oasis:entry colname="col12"><bold>0.939</bold></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Cl<inline-formula><mml:math id="M116" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Ca<inline-formula><mml:math id="M117" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Frisbee</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.859</bold></oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Frisbee</oasis:entry>  
         <oasis:entry colname="col8">0.138</oasis:entry>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Larch</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.762</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.751</bold></oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Larch</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.700</bold></oasis:entry>  
         <oasis:entry colname="col9">0.330</oasis:entry>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Left</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.875</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.787</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.884</bold></oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Left</oasis:entry>  
         <oasis:entry colname="col8">0.278</oasis:entry>  
         <oasis:entry colname="col9">0.571</oasis:entry>  
         <oasis:entry colname="col10">0.102</oasis:entry>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Sandwich</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.649</bold></oasis:entry>  
         <oasis:entry colname="col3">0.539</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.941</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.851</bold></oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Sandwich</oasis:entry>  
         <oasis:entry colname="col8">0.226</oasis:entry>  
         <oasis:entry colname="col9">0.433</oasis:entry>  
         <oasis:entry colname="col10">0.354</oasis:entry>  
         <oasis:entry colname="col11">0.274</oasis:entry>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Strange</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.774</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.680</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.751</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.889</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.746</bold></oasis:entry>  
         <oasis:entry colname="col7">Strange</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.772</bold></oasis:entry>  
         <oasis:entry colname="col9">0.419</oasis:entry>  
         <oasis:entry colname="col10"><bold>0.723</bold></oasis:entry>  
         <oasis:entry colname="col11">0.340</oasis:entry>  
         <oasis:entry colname="col12">0.566</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">SO<inline-formula><mml:math id="M118" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">NH<inline-formula><mml:math id="M119" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Frisbee</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.745</bold></oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Frisbee</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.715</bold></oasis:entry>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Larch</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M120" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.056</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M121" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.007</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Larch</oasis:entry>  
         <oasis:entry colname="col8"><bold>0.605</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.619</bold></oasis:entry>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Left</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.740</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.836</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M122" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.271</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Left</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M123" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.135</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M124" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.250</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10">0.261</oasis:entry>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Sandwich</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M125" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.415</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M126" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.388</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">0.134</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M127" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.285</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Sandwich</oasis:entry>  
         <oasis:entry colname="col8">0.000</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M128" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.003</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M129" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.256</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col11"><inline-formula><mml:math id="M130" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.103</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Strange</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.731</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.728</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M131" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.133</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.958</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M132" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.318</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">Strange</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M133" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.449</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M134" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.040</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M135" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.277</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col11"><inline-formula><mml:math id="M136" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.024</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col12"><inline-formula><mml:math id="M137" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.325</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Na<inline-formula><mml:math id="M138" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">NO<inline-formula><mml:math id="M139" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Frisbee</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.863</bold></oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Frisbee</oasis:entry>  
         <oasis:entry colname="col8">0.000</oasis:entry>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Larch</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.667</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.625</bold></oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Larch</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M140" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.087</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9">0.320</oasis:entry>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Left</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.875</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.765</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.818</bold></oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Left</oasis:entry>  
         <oasis:entry colname="col8">0.404</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M141" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.346</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M142" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.366</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Sandwich</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.777</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.643</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.920</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.948</bold></oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">Sandwich</oasis:entry>  
         <oasis:entry colname="col8">0.136</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M143" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.011</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10">0.295</oasis:entry>  
         <oasis:entry colname="col11"><inline-formula><mml:math id="M144" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.289</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Strange</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.843</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.682</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.711</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.963</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.897</bold></oasis:entry>  
         <oasis:entry colname="col7">Strange</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M145" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.294</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M146" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.133</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10">0.353</oasis:entry>  
         <oasis:entry colname="col11"><inline-formula><mml:math id="M147" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.504</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col12">0.292</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry rowsep="1" colname="col1">K<inline-formula><mml:math id="M148" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry rowsep="1" colname="col2"/>  
         <oasis:entry rowsep="1" colname="col3"/>  
         <oasis:entry rowsep="1" colname="col4"/>  
         <oasis:entry rowsep="1" colname="col5"/>  
         <oasis:entry rowsep="1" colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Frisbee</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.847</bold></oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Larch</oasis:entry>  
         <oasis:entry colname="col2">0.561</oasis:entry>  
         <oasis:entry colname="col3">0.490</oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Left</oasis:entry>  
         <oasis:entry colname="col2">0.401</oasis:entry>  
         <oasis:entry colname="col3">0.261</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.584</bold></oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Sandwich</oasis:entry>  
         <oasis:entry colname="col2">0.428</oasis:entry>  
         <oasis:entry colname="col3">0.562</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.794</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.523</bold></oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Strange</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.614</bold></oasis:entry>  
         <oasis:entry colname="col3">0.563</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.834</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.734</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.725</bold></oasis:entry>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup><?xmltex \end{scaleboxenv}?></oasis:table></table-wrap>

</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results</title>
<sec id="Ch1.S3.SS1">
  <title>Spatial and temporal variability of pond chemistry</title>
      <p id="d1e3400">Medians of temporal deviation scores significantly exceeded the median
spatial deviation scores in several chemical species (Cl<inline-formula><mml:math id="M149" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>,
SO<inline-formula><mml:math id="M150" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, Na<inline-formula><mml:math id="M151" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M152" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Ca<inline-formula><mml:math id="M153" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>; Fig. 2), but there was no
significant difference between the median spatial and temporal deviation
scores for DON, Mg<inline-formula><mml:math id="M154" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, NH<inline-formula><mml:math id="M155" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, and NO<inline-formula><mml:math id="M156" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>. For species that
were significantly more temporally variable than spatially variable,
concentrations among ponds, despite differences in magnitude, tended to be
strongly positively correlated which each other (<inline-formula><mml:math id="M157" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.01</mml:mn></mml:mrow></mml:math></inline-formula>) with the notable
exception of DON (Table 2). NO<inline-formula><mml:math id="M158" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and NH<inline-formula><mml:math id="M159" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> were not
significantly correlated to any other species (<inline-formula><mml:math id="M160" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">0.01</mml:mn></mml:mrow></mml:math></inline-formula>) (Table 3), while
all other species tended to be strongly positively correlated which each
other (<inline-formula><mml:math id="M161" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.01</mml:mn></mml:mrow></mml:math></inline-formula>), although there were some exceptions. Spatial deviations
did not significantly exceed temporal deviations for any chemical species.</p>
</sec>
<sec id="Ch1.S3.SS2">
  <title>Seasonal patterns in pond water chemistry</title>
      <p id="d1e3561">Pond water chemistry varied not only among ponds but also throughout the season
(Fig. 3). Throughout 2015, the temporal trend of pond mean-normalized
concentrations in the six ponds appeared to have a spatial coherency in DON,
Cl<inline-formula><mml:math id="M162" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M163" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, Na<inline-formula><mml:math id="M164" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M165" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and Mg<inline-formula><mml:math id="M166" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> concentrations.
There was a gradual increase in concentrations of these species from DOY 140
to 260, punctuated by small decline in concentrations following a large storm
on DOY 185–188, followed by a gradual decrease from DOY 260 to the end of
the season. Ca<inline-formula><mml:math id="M167" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> displayed a contrasting temporal trajectory to the
other chemical species, decreasing from DOY 190 to the end of the season,
while NO<inline-formula><mml:math id="M168" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and NH<inline-formula><mml:math id="M169" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> appeared to have no coherent pattern
relative to the other chemical species. Generally, ponds were closest to
their mean values during the mid-season (DOY 200–250) and pond-mean
normalized concentrations differed the least among ponds during this time,
being more divergent earlier (DOY 140–200) and later (DOY 250–300) in the
season.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T3" specific-use="star"><caption><p id="d1e3658">Correlation coefficients among chemical species for all ponds.
Values are bolded when the correlation is significant at the <inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">0.01</mml:mn></mml:mrow></mml:math></inline-formula>
level.</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="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Species</oasis:entry>  
         <oasis:entry colname="col2">DON</oasis:entry>  
         <oasis:entry colname="col3">Cl<inline-formula><mml:math id="M171" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">SO<inline-formula><mml:math id="M172" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5">Na<inline-formula><mml:math id="M173" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">K<inline-formula><mml:math id="M174" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">Mg<inline-formula><mml:math id="M175" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8">Ca<inline-formula><mml:math id="M176" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9">NH<inline-formula><mml:math id="M177" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Cl<inline-formula><mml:math id="M178" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.710</bold></oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SO<inline-formula><mml:math id="M179" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.594</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.827</bold></oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Na<inline-formula><mml:math id="M180" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.615</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.971</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.802</bold></oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">K<inline-formula><mml:math id="M181" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">0.276</oasis:entry>  
         <oasis:entry colname="col3"><bold>0.504</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.462</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.595</bold></oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Mg<inline-formula><mml:math id="M182" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.563</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.892</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.787</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.940</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.585</bold></oasis:entry>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Ca<inline-formula><mml:math id="M183" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.605</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.408</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.531</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.285</bold></oasis:entry>  
         <oasis:entry colname="col6">0.000</oasis:entry>  
         <oasis:entry colname="col7">0.166</oasis:entry>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NH<inline-formula><mml:math id="M184" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M185" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.097</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.034</oasis:entry>  
         <oasis:entry colname="col4">0.039</oasis:entry>  
         <oasis:entry colname="col5">0.000</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M186" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.163</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">0.027</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M187" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.082</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NO<inline-formula><mml:math id="M188" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M189" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.134</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M190" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.201</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M191" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.143</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M192" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.207</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M193" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.076</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M194" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.158</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M195" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.078</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9">0.218</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><caption><p id="d1e4209">Pond normalized concentrations of all measured chemical species in
each pond and precipitation for the 2015 snow-free season. In chemical
species on left side of the panel (Cl<inline-formula><mml:math id="M196" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M197" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, Na<inline-formula><mml:math id="M198" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>,
K<inline-formula><mml:math id="M199" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Ca<inline-formula><mml:math id="M200" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>) temporal variation exceeds spatial variation, and no
significant difference is present for species on the right (DON, Mg<inline-formula><mml:math id="M201" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>,
NH<inline-formula><mml:math id="M202" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, NO<inline-formula><mml:math id="M203" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f03.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS3">
  <title>Pond hydrology and linkages with water chemistry</title>
      <p id="d1e4317">As was observed for water chemistry, there was also a seasonal pattern in
pond hydrologic storage (Fig. 4). In general, ponds were full following
snowmelt, with water levels generally declining throughout the season and
eventually rising again in late summer. Catchments showed synchronous runoff
responses to two major rain events on DOY 166 and 185 and three smaller rain
events between DOY 260 and 290, although the magnitude of response varied.
Following the early-season rain events, Left pond and Strange pond
experienced prolonged summer drawdown, while this drawdown was less pronounced
in Larch, Frisbee, and Sandwich ponds. At DOY 250 all ponds began a gradual
increase in stage continuing to the end of season but did not return to
post-snowmelt levels. Within these five study ponds with recorded depth,
there appeared to be no clear relationship between variation in stage and
pond geometry (depth, shoreline development, area, or perimeter; Table 1).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4" specific-use="star"><caption><p id="d1e4322">Precipitation (vertical bars, top panel), as well as depth of water
column (continuous line) and runoff depths (vertical bars) in each of the
instrumented study ponds over the 2015 ice-free season.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f04.pdf"/>

        </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T4" specific-use="star"><caption><p id="d1e4334">Values of <inline-formula><mml:math id="M204" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and root mean square error (RMSE) from the
curve <inline-formula><mml:math id="M205" display="inline"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:mo>]</mml:mo><mml:mo>=</mml:mo><mml:mstyle displaystyle="false"><mml:mfrac style="text"><mml:mrow><mml:mo>[</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mi mathvariant="normal">st</mml:mi></mml:msub><mml:mo>]</mml:mo></mml:mrow><mml:mover accent="true"><mml:mrow><mml:mo>[</mml:mo><mml:msub><mml:mi>x</mml:mi><mml:mtext>s</mml:mtext></mml:msub><mml:mo>]</mml:mo></mml:mrow><mml:mo mathvariant="normal">‾</mml:mo></mml:mover></mml:mfrac></mml:mstyle><mml:mo>=</mml:mo><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>(</mml:mo><mml:mi mathvariant="normal">stage</mml:mi><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for each set of normalized
concentration data, <inline-formula><mml:math id="M206" display="inline"><mml:mrow><mml:mo>[</mml:mo><mml:mi>x</mml:mi><mml:mo>]</mml:mo></mml:mrow></mml:math></inline-formula>. Chemical species were manually classified as
hydrologically driven if they shared a common (approximate) <inline-formula><mml:math id="M207" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> value
within a pond with a low RMSE relative to other species in the same pond.
Notable exceptions to the general classification in the table heading are
bolded.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="10">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right" colsep="1"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry rowsep="1" namest="col2" nameend="col6" align="center" colsep="1">Hydrologically driven </oasis:entry>  
         <oasis:entry rowsep="1" namest="col7" nameend="col10" align="center">Not hydrologically driven </oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">DON</oasis:entry>  
         <oasis:entry colname="col3">Cl<inline-formula><mml:math id="M208" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">Na<inline-formula><mml:math id="M209" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5">K<inline-formula><mml:math id="M210" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">Mg<inline-formula><mml:math id="M211" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">Ca<inline-formula><mml:math id="M212" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8">NH<inline-formula><mml:math id="M213" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col9">NO<inline-formula><mml:math id="M214" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10">SO<inline-formula><mml:math id="M215" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row rowsep="1">  
         <oasis:entry namest="col1" nameend="col10">Frisbee </oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M216" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M217" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.61</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M218" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.63</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M219" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.01</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M220" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.52</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M221" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>2.15</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M222" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.38</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M223" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.23</oasis:entry>  
         <oasis:entry colname="col9">0.23</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M224" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.11</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">RMSE</oasis:entry>  
         <oasis:entry colname="col2">0.27</oasis:entry>  
         <oasis:entry colname="col3">0.16</oasis:entry>  
         <oasis:entry colname="col4">0.15</oasis:entry>  
         <oasis:entry colname="col5">0.22</oasis:entry>  
         <oasis:entry colname="col6">0.23</oasis:entry>  
         <oasis:entry colname="col7">0.25</oasis:entry>  
         <oasis:entry colname="col8">0.70</oasis:entry>  
         <oasis:entry colname="col9">0.29</oasis:entry>  
         <oasis:entry colname="col10">0.24</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry namest="col1" nameend="col10">Larch </oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M225" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M226" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.35</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M227" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.28</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M228" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.29</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M229" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.38</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M230" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.44</oasis:entry>  
         <oasis:entry colname="col7">0.39</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M231" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.73</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M232" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.18</oasis:entry>  
         <oasis:entry colname="col10">0.08</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">RMSE</oasis:entry>  
         <oasis:entry colname="col2">0.16</oasis:entry>  
         <oasis:entry colname="col3">0.06</oasis:entry>  
         <oasis:entry colname="col4">0.09</oasis:entry>  
         <oasis:entry colname="col5">0.09</oasis:entry>  
         <oasis:entry colname="col6">0.08</oasis:entry>  
         <oasis:entry colname="col7">0.14</oasis:entry>  
         <oasis:entry colname="col8">0.65</oasis:entry>  
         <oasis:entry colname="col9">0.29</oasis:entry>  
         <oasis:entry colname="col10">0.52</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry namest="col1" nameend="col10">Left </oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M233" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M234" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.70</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M235" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.20</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M236" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.07</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M237" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.21</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M238" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.05</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math id="M239" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.12</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M240" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.44</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M241" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.29</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M242" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.30</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">RMSE</oasis:entry>  
         <oasis:entry colname="col2">0.28</oasis:entry>  
         <oasis:entry colname="col3">0.19</oasis:entry>  
         <oasis:entry colname="col4">0.14</oasis:entry>  
         <oasis:entry colname="col5">0.19</oasis:entry>  
         <oasis:entry colname="col6">0.16</oasis:entry>  
         <oasis:entry colname="col7">0.15</oasis:entry>  
         <oasis:entry colname="col8">0.52</oasis:entry>  
         <oasis:entry colname="col9">0.38</oasis:entry>  
         <oasis:entry colname="col10">0.35</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry namest="col1" nameend="col10">Sandwich </oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M243" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M244" display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.47</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M245" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.43</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M246" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.53</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M247" display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.28</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M248" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.63</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">0.36</oasis:entry>  
         <oasis:entry colname="col8">0.82</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math id="M249" display="inline"><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">0.35</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col10">0.85</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">RMSE</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.19</bold></oasis:entry>  
         <oasis:entry colname="col3">0.08</oasis:entry>  
         <oasis:entry colname="col4">0.05</oasis:entry>  
         <oasis:entry colname="col5"><bold>0.15</bold></oasis:entry>  
         <oasis:entry colname="col6">0.07</oasis:entry>  
         <oasis:entry colname="col7">0.30</oasis:entry>  
         <oasis:entry colname="col8">0.78</oasis:entry>  
         <oasis:entry colname="col9">0.28</oasis:entry>  
         <oasis:entry colname="col10">0.66</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry namest="col1" nameend="col10">Strange </oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M250" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math id="M251" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.16</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math id="M252" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.75</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M253" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.55</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math id="M254" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.23</oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math id="M255" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.57</oasis:entry>  
         <oasis:entry colname="col7">0.42</oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math id="M256" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.08</oasis:entry>  
         <oasis:entry colname="col9">0.07</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math id="M257" display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.71</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">RMSE</oasis:entry>  
         <oasis:entry colname="col2">0.37</oasis:entry>  
         <oasis:entry colname="col3">0.18</oasis:entry>  
         <oasis:entry colname="col4">0.11</oasis:entry>  
         <oasis:entry colname="col5">0.11</oasis:entry>  
         <oasis:entry colname="col6">0.15</oasis:entry>  
         <oasis:entry colname="col7">0.24</oasis:entry>  
         <oasis:entry colname="col8">0.45</oasis:entry>  
         <oasis:entry colname="col9">0.13</oasis:entry>  
         <oasis:entry colname="col10"><bold>0.18</bold></oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e5243">Generally, DON, Cl<inline-formula><mml:math id="M258" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M259" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M260" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and Mg<inline-formula><mml:math id="M261" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> were classified as
the hydrologically driven chemical species and Ca<inline-formula><mml:math id="M262" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, NH<inline-formula><mml:math id="M263" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>,
NO<inline-formula><mml:math id="M264" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, and SO<inline-formula><mml:math id="M265" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> were classified as non-hydrologically driven
(Table 4; Fig. 5). There were few exceptions to this general classification;
most notably, DON and K<inline-formula><mml:math id="M266" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> tended to slightly poorer fits (larger RMSE;
slightly less hydrologically driven) in Sandwich pond, whereas SO<inline-formula><mml:math id="M267" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>
may have been hydrologically driven in Strange pond. Slight differences in
<inline-formula><mml:math id="M268" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="italic">β</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> values among ponds for hydrologically driven species are
influenced by the differences in bathymetry, which
dictates the stage–volume relationship.</p>
</sec>
<sec id="Ch1.S3.SS4">
  <title>Principal component analysis</title>
      <p id="d1e5378">PCA allowed for a reduction in the redundancy of species that are highly
correlated (Table 3) and the clustering of samples from each pond in PC space
(Fig. 6). The analysis also shows a clustering of chemical species along the
PC axes. A collection of the hydrologically driven chemical species (Table 4;
DON, Mg<inline-formula><mml:math id="M269" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M270" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M271" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Cl<inline-formula><mml:math id="M272" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> closely follows the PC1 axis
with slightly negative scores for PC2. Two other non-hydrologically driven
chemical species have positive scores along PC1 with slightly negative
(SO<inline-formula><mml:math id="M273" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and positive (Ca<inline-formula><mml:math id="M274" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> scores along PC2. Inorganic nitrogen
species, (NO<inline-formula><mml:math id="M275" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and NH<inline-formula><mml:math id="M276" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, also non-hydrologically driven,
have negative scores along the PC2 axis and slightly negative scores along
PC1. The spread of data points for Strange pond, Left pond, and Frisbee pond
are more elongate along the PC1 axis where the spread of data from Larch
pond, Erin pond, and Sandwich pond are aligned along the PC2 axis. Temporally,
the data tend to move from the upper-left quadrant (positive scores for PC2,
negative scores for PC1) to the lower-right quadrant (positive scores for
PC1, negative scores for PC2) over the course of the season. Chemical species
which were classified as hydrologically driven (Table 4) were not necessarily
the same species which showed that temporal variance exceeded spatial
variance (Fig. 2). DON and Mg<inline-formula><mml:math id="M277" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> were classified as hydrologically driven
but did not have the same degree of temporal coherence displayed by Cl<inline-formula><mml:math id="M278" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>,
Na<inline-formula><mml:math id="M279" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and K<inline-formula><mml:math id="M280" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>. Conversely, Ca<inline-formula><mml:math id="M281" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> and SO<inline-formula><mml:math id="M282" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> display
significantly greater temporal variability then spatial variability but were
not classified as hydrologically driven constituents. Strange, Left, and
Frisbee ponds were elongated with respect to the PC1 axis, which corresponds
closely with the group of chemical species that are hydrologically driven.
Strange and Left ponds showed the greatest variation in pond stage (Table 1;
Fig. 4), linking the hydrological variation with the variation in
concentrations of chemical species controlled by stage. Frisbee pond showed
less variation in stage but was elongate with the respect to the axis of the
hydrologically driven species cluster, suggesting that variation in pond
stage alone does not necessarily dictate which species are most chemodynamic
within a pond. Larch and Sandwich ponds, which showed lesser variation in
stage, were elongated with respect to PC2, orthogonal to the cluster of
hydrologically driven species along PC1. The redundancy in the original
dataset is primarily due to the clustering of the hydrologically driven
species along PC1, and the very close clustering of Na<inline-formula><mml:math id="M283" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> and Cl<inline-formula><mml:math id="M284" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula> in
PC space (indicating the marine halite influence on these ponds; Bos and
Pellatt, 2012). In addition, the decoupling of Mg<inline-formula><mml:math id="M285" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> and Ca<inline-formula><mml:math id="M286" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>
trajectories (Fig. 3) and in PC space (Fig. 6) indicates the potential role of
Ca<inline-formula><mml:math id="M287" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> in either carbonate cycling associated with productivity and carbon
dioxide intake (Macrae et al., 2004), precipitation, or cation substitution
(Wetzel, 2001). Further, not only are the hydrologically driven species
(Table 4) correlated among ponds (Table 2), but they are also correlated
among species (Table 3). The apparent redundancy of several of these chemical
trajectories is observed in the normalized time series of concentration data,
with many of the species which align along PC1 axis showing similar
concentration trajectories at the seasonal (Fig. 3) and event (Fig. 7)
scales.</p>
</sec>
<sec id="Ch1.S3.SS5">
  <title>Event-scale variation in pond chemistry</title>
      <p id="d1e5611">In addition to being highly chemodynamic over the course of an ice-free
season, pond chemistry varied greatly over the course of a single
storm-runoff event (Fig. 7). For samples taken during and following the
storm event in Strange pond on DOY 185–188, concentrations of some chemical
species varied by the same magnitude over the course of several days as they
did over the period of the entire ice-free season (DON, K<inline-formula><mml:math id="M288" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Ca<inline-formula><mml:math id="M289" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>,
NO<inline-formula><mml:math id="M290" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>; other species varied but not to the same extent (Cl<inline-formula><mml:math id="M291" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>,
SO<inline-formula><mml:math id="M292" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, Na<inline-formula><mml:math id="M293" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Mg<inline-formula><mml:math id="M294" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, NH<inline-formula><mml:math id="M295" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>; Table S2). In Frisbee pond,
chemical species tended to vary by a similar magnitude over the storm period
as they did over the entire season and this was not restricted to DON,
K<inline-formula><mml:math id="M296" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and Ca<inline-formula><mml:math id="M297" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5"><caption><p id="d1e5730">Comparison of the stage–concentration relationship in a
<bold>(a)</bold> hydrologically driven chemical species (Cl<inline-formula><mml:math id="M298" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, in Frisbee
pond), and <bold>(b)</bold> a non-hydrologically driven species (NH<inline-formula><mml:math id="M299" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, in
Larch pond).</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f05.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6" specific-use="star"><caption><p id="d1e5768">Principal components analysis of chemical concentrations in all
ponds throughout the 2015 snow-free season. The sampling date corresponds to
the colour ramp with earlier dates in blue and later dates in red. PC1
primarily corresponds with the hydrologically driven chemical species, while
PC2 corresponds to inorganic nitrogen species (NO<inline-formula><mml:math id="M300" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, NH<inline-formula><mml:math id="M301" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>.
The hollow symbols are highlighted with solid points.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f06.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7"><caption><p id="d1e5806">Short-term variation in DON, Cl<inline-formula><mml:math id="M302" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M303" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, and
NO<inline-formula><mml:math id="M304" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> concentrations in <bold>(a)</bold> Frisbee pond and
<bold>(b)</bold> Strange pond during a rain event on 3 to 6 July 2015 (DOY
185–188, highlighted with red bars).</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f07.pdf"/>

        </fig>

</sec>
</sec>
<sec id="Ch1.S4">
  <title>Discussion</title>
<sec id="Ch1.S4.SS1">
  <title>Seasonal and spatial variability in pond chemistry</title>
      <p id="d1e5869">Ponds in this study displayed a coherent trend in several chemical
concentrations over an ice-free season, despite differences in pond geometry,
catchment characteristics, and absolute magnitude of chemical concentrations.
Landscape-scale factors such as climate are controlling hydrological
processes and, in turn, concentrations of chemical species (specifically,
Cl<inline-formula><mml:math id="M305" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M306" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M307" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Mg<inline-formula><mml:math id="M308" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, and dissolved organic nitrogen).
Magnuson et al. (1990) and Baines et al. (2000) reported Ca<inline-formula><mml:math id="M309" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> to be
temporally coherent among groups of large lakes in Wisconsin, USA, consistent
with our findings, while Magnuson et al. (1990) found K<inline-formula><mml:math id="M310" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> or
SO<inline-formula><mml:math id="M311" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula> to lack coherence, contrasting with our results. However, the
absolute magnitudes of different chemical species concentrations varied among
ponds despite similar trajectories of mean-normalized concentrations. This
suggests that influences such as runoff inputs, evapoconcentration,
bathymetry, and internal processes (sediment–water interaction and biological
cycling) may be driving these absolute differences while preserving seasonal
trajectories relative to a pond mean value. Other authors have reported on
local spatial heterogeneity of biogeochemical properties of ponds, such as
the conditions of nutrient limitation of primary productivity in different
lakes (Hogan et al., 2014; Symons et al., 2012). This work suggests that the
seasonal trajectory of concentration of at least some chemical species are
not reflective of this spatial variability and instead more reflective of
landscape-level processes.</p>
      <p id="d1e5948">The importance of biogeochemical and hydrological processes can be informed
by the location of (a) clusters of samples from individual ponds and
(b) ordination of chemical species in PCA space. In many of the same study
ponds as this work, White et al. (2014) found similar clustering of Cl<inline-formula><mml:math id="M312" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>,
Na<inline-formula><mml:math id="M313" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M314" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and Mg<inline-formula><mml:math id="M315" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> along their first PC axis (most variance
explained) and another cluster including NH<inline-formula><mml:math id="M316" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> and NO<inline-formula><mml:math id="M317" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula> along
their second axes. In contrast, total nitrogen was approximately orthogonal
to both those clusters, instead of being aligned with the other species which
were identified as hydrologically driven in our analysis. Differences between
the findings of White et al. (2014) and this work may be explained by the
inclusion of additional limnological measurements into the PCA, the greater
number of lakes in their study  (20), the smaller number of samples taken at
each lake per year (3), and the reporting of total N as opposed to the
dissolved fraction. Sokal et al. (2010) did not report a similar clustering
of chemical species in PC space, with total Kjeldahl nitrogen (TKN),
Cl<inline-formula><mml:math id="M318" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M319" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Mg<inline-formula><mml:math id="M320" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, and K<inline-formula><mml:math id="M321" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> showing great variation relative to
the tight clustering found in this study in the Slave River delta and with
less separation from the non-hydrologically driven chemical species in our
study (Ca<inline-formula><mml:math id="M322" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M323" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>). This could be due to larger and deeper
lakes studied in the region (<inline-formula><mml:math id="M324" display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M325" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">6</mml:mn></mml:msup></mml:math></inline-formula> m<inline-formula><mml:math id="M326" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> surface area; 1.5 m
deep) in addition to additional limnological and isotopic measurements into
the PCA. However, this difference in species clustering may not be
region-specific as Wiklund et al. (2012) found a clustering of Na<inline-formula><mml:math id="M327" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>,
Cl<inline-formula><mml:math id="M328" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, TKN, K<inline-formula><mml:math id="M329" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and Mg<inline-formula><mml:math id="M330" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> in PC space from lakes in the Peace
Athabasca Delta region. Wiklund et al. (2012) also report approximately equal
angles between vectors of (a) the cluster of hydrologically driven chemical
species and (b) Ca<inline-formula><mml:math id="M331" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> and SO<inline-formula><mml:math id="M332" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, as was found in this study.</p>
</sec>
<sec id="Ch1.S4.SS2">
  <title>Event-scale variation in pond chemistry</title>
      <p id="d1e6180">Short-term variation in concentrations during a storm was pronounced in
Frisbee pond during the storm of DOY 185–188 in 2015. This is likely due to
the difference in the proportion of new water entering the pond relative to
the volume of old water in the pond. In Frisbee pond, the rainfall inputs
represent a much greater fraction of the total pond water at the conclusion
of the event (nearly one-half), compared to Strange pond, which is larger and
more full of water pre-event, where event water represents a smaller
proportion of the total post-event water (approximately one-quarter) despite
the lesser runoff amount (Fig. 4). This leads to the dampening of the
storm-based concentration variability in Strange pond. Those species that may
have elevated concentrations in event water relative to lower concentrations
in pond water, such as DON (Morison et al., 2017), show a heightened response
in terms of pond concentrations in both Frisbee pond and Strange pond.
Species which have event water concentrations which are similar to background
pond water concentrations show a dampened response. Although the volume of
event water being added may not represent a great fraction of the total water
in the pond, it is enriched in species that occur naturally in rainwater or
through primary runoff pathways (shallow, organic subsurface material). This
agrees with the findings of Abnizova (2013), which showed that the ionic
composition on the event scale of runoff water to ponds in high-Arctic
wetlands was caused by the vegetative structure of the catchment (related to
dissolved organic material) and bedrock composition.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8"><caption><p id="d1e6185">Graphical summation of major findings from this study;
<bold>(a)</bold> factors driving hydrological control of particular chemical
species in ponds, <bold>(b)</bold> hypothesized factors driving temporal
coherence in chemical species in ponds, and <bold>(c)</bold> short-term variation
in hydrochemistry can exceed seasonal-scale variation despite the large
difference in timescales.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/14/5471/2017/bg-14-5471-2017-f08.pdf"/>

        </fig>

<?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S4.SS3">
  <title>Inferring hydrological and biogeochemical process from patterns in pond
chemistry</title>
      <p id="d1e6211">This study does not aim to present direct measurements of any biogeochemical
process, including the magnitude and direction of which
biogeochemical transformations are operating to which extent. Each chemical
species measured in this study in subject to differing degrees of
reactivity/conservativism. Future research is needed to elucidate the
individual or coupled cycling processes of these elements in subarctic
freshwater ecosystems. Chemical species which appear to be driven primarily
by non-hydrological processes (Table 4) are likely those which are most
reactive. However, our results can be contextualized within the existing body
of knowledge of hydrobiogeochemical processes which have been measured in
similar environments previously to determine if our observations are
consistent with previous findings of different species.</p>
      <p id="d1e6214">Biogeochemical variations large in magnitude also often occur on short
timescales, which are typically associated with the movement of water across
geochemical boundaries (McClain et al., 2003). Previous work in tundra and
high-Arctic environments have shown pathways for transformations of runoff
water through the catchments, including biological incorporation of nutrients
(Thompson and Woo, 2009) and geochemical processes of weathering and ion
exchange (Quinton and Pomeroy, 2006), which impact the quality of the runoff
water arriving at the pond. Once the runoff water is delivered to the ponds,
the biological factors driving responses to the incorporation and sedimentary
burial of nitrogen and phosphorus on short timescales (<inline-formula><mml:math id="M333" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 72 h of return
to pre-event levels) were demonstrated experimentally by Eichel et
al. (2014). These observations are consistent with the increase in nutrient
concentrations followed by rapid uptake to pre-event levels which was
observed during and following the storm event around DOY 185 (Fig. 7) in this
study. These mechanisms of runoff contributions to pond chemical variability
are important for future studies that aim to use seasonal and interannual
variations in pond and lake chemistries to examine changing flow paths in
thawing permafrost environments. The relative change of concentrations in
ponds and lakes over events, seasons, and years will be a product of the
difference in concentrations between new and old water and the degree of
dilution of new water arriving at the pond. If the concentration of a
constituent in old water is not significantly different from that in new
water, future work which infers changing flow paths from changing chemical concentrations over time may
significantly underestimate the degree of change to the movement of water and
solutes due to thawing permafrost (Lougheed et al., 2011). Conversely, it is
also possible to overestimate the change in flow paths delivering solutes
which are radically different in concentration from old water. In this work,
no clear relationship between chemical trajectory (Fig. 3) and runoff
(Fig. 4) was observed, nor were either of these related specifically to total
catchment area (Table 1). However, this may be a result of the variable
source area concept applying in this fill-and-spill system (Spence et al.,
2010; Morison et al., 2017), in which substantial portions of the catchment
are not contributing runoff to the ponds for certain storms which do not
provide requisite overfilling of the catchment storage capacity threshold.
This effect renders estimates of total catchment area which are delineated by
topography less useful without additional knowledge of total subsurface
storage capacity and effective contributing area for each runoff event.</p>
      <p id="d1e6224">The method of fitting curves to stage–concentration relations to manually
determine the degree to which evapoconcentration and dilution dictates
chemical concentrations may not capture all of the complex dynamics related
to hydrological controls. For example, pond volume controls diurnal
temperature fluctuation amplitude and indirectly the rate of biogeochemical
processes. In northern tundra environments, low temperatures limit the rates
at which biogeochemical processes occur (Stark, 2007). Microbial
decomposition remains the crucial bottleneck (rate limiting step) in nutrient
cycling (Stark, 2007; Andersen et al., 2013). Temperatures are often the most
important factor limiting the rate of microbial decomposition of organic
matter in cold-region aquatic and terrestrial ecosystems (Wallenstein et al.,
2009; Vonk et al., 2015; Wickland et al., 2012). On the north shore of
Alaska, Koch et al. (2014) showed that the chemical dynamics were less
pronounced in larger ponds with greater storage capacity which maintained
lower temperatures, limiting evaporation (and therefore evapoconcentration)
as well as retarding biological uptake. Some of these processes may explain
some discrepancies between the classified hydrologically driven chemical
species and those species for which temporal variability exceeded spatial
variability.</p>
</sec>
<sec id="Ch1.S4.SS4">
  <title>Implications for sampling design in future studies</title>
      <p id="d1e6233">Generally, the current standards of infrequent measurements per annum are
unlikely to be sufficient to capture the variability in highly chemodynamic
systems, such as shallow ponds in which storage varies by up to 80 % of
the mean value over the course of the ice-free season. In contrast, and
campaigns that may be more temporally coarse but spatially intensive are
applicable for larger, less chemodynamic lakes and ponds, in which total
water inputs and outputs represent a much smaller proportion of the total
volume. Further, the synchrony in the chemical behaviour of some spices
(Cl<inline-formula><mml:math id="M334" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M335" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M336" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M337" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, Ca<inline-formula><mml:math id="M338" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>) in these ponds
suggests potential redundancy in the sampling of a great deals of lakes if
the research goals are related to the measurement of these chemical species.
This study may be subject to different limitations by observing water column
chemistry in only six lakes over the ice-free season. However, it appears these
six ponds capture a representative range of chemical concentrations, spanning
1–2 orders of magnitude (Table S2), which are representative of much wider
spatial surveys in much of the work outlined in Table S1 (and, more
specifically, in line with the variance observed by other authors who have
studied ponds in our specific region (Bos and Pellatt, 2012; White et al.,
2014; Jacques et al., 2016). The fact that these ponds are closely spatially
clustered may remove effects of microclimates on the scales of 10–100 km,
which may reduce the degree of synchrony observed in chemical concentrations,
due to different precipitation, runoff, and evaporative drawdown regimes.
Further, the very shallow and small nature of these ponds in this work,
although comprising the majority of surface water features in permafrost
landscapes (Muster et al., 2013), may not reflect the chemostatic nature of
larger lakes in permafrost regions. Larger lakes, with a much greater total
volumetric storage capacity, would be generally subject to hydrologic fluxes
(evaporation, precipitation, inflows) which represent a much smaller
proportion of total water storage on both annual and individual rain event
timescales. This would result in the hydrodynamics and associated changes to
hydrochemical concentrations to be dampened in these larger lakes relative to
our highly chemodynamic systems.</p>
      <p id="d1e6290">Future biogeochemical research must consider the relative terms in the water
balance in a pond to determine periods of greatest variability (such as
snowmelt vs. rainwater dominated ponds; e.g. Bouchard et al., 2013). A water
budget approach should be incorporated into future studies which attempt to
use changing solute concentrations as a proxy for changes to ensure that
appropriate hydrological weighting to changes of concentrations in surface
water are properly represented. Alternately, approaches characterizing total
mass depletion of different ions and nutrients (e.g. Koch et al., 2014), an
evaporative normalization factor (e.g. Borghini et al., 2013), the use of the
Shannon index in a hydrochemical context (Thompson and Woo, 2009), and hydrologic
inference through isotopic composition (e.g. White et al., 2014) may provide
a hydrologic context to concentration measurements which is lacking
otherwise.</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <title>Conclusions</title>
      <p id="d1e6301">This study reported on the degree of hydrologic control on nutrient and major
ion chemistry of a set of six of small (<inline-formula><mml:math id="M339" display="inline"><mml:mo>&lt;</mml:mo></mml:math></inline-formula> 1 ha), shallow permafrost ponds
in the Hudson Bay Lowlands. Generally speaking, temporal variability exceeds
spatial variability in pond chemistry in this landscape. Five chemical
species (Cl<inline-formula><mml:math id="M340" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M341" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, Na<inline-formula><mml:math id="M342" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M343" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and Ca<inline-formula><mml:math id="M344" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> showed a
temporal coherence in six different ponds over the course of an ice-free
season (Fig. 8). No pond demonstrated a spatial coherence in concentration
trajectory which was distinct from every other pond. A set of species was
determined to be hydrologically controlled (DON, Cl<inline-formula><mml:math id="M345" display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, Na<inline-formula><mml:math id="M346" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, K<inline-formula><mml:math id="M347" display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>
and Mg<inline-formula><mml:math id="M348" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, either directly through processes of evapoconcentration and
inflow/precipitation dilution or indirectly through pond hydrology exerting
an influence on other environmental controls such as temperature regimes,
which influence biogeochemical characteristics. Approaches of PCA and
coherence/correlation showed that these hydrologically driven chemical
species are strongly correlated to each other and among ponds. This evidence
suggests that landscape-level controls on pond hydrology may reduce the
spatial heterogeneity in pond chemical trajectories for the hydrologically
driven chemical species, but not for those species that are not
hydrologically controlled (Ca<inline-formula><mml:math id="M349" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula>, SO<inline-formula><mml:math id="M350" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula>, NO<inline-formula><mml:math id="M351" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>,
NH<inline-formula><mml:math id="M352" display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mo>+</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. Further, on the event scale, variation over the course of days
during and following precipitation events may be approximately
equal to the variation over the course of months. This longer period
variation is also not limited to the hydrologically driven species,
indicating the importance of biogeochemically active periods coinciding with
periods of water movement across boundaries (catchment–pond interactions).
This work has important implications for understanding the highly
chemodynamic behaviour of small, shallow permafrost ponds over both
short-term and long-term temporal scales while remaining spatially
synchronous. Our findings indicate that the design of future sampling regimes
which continue to rely on inference from broad spatial sampling on coarse
temporal scales must consider the hydrologic context of the samples taken. In
particular, the proximity of recent rain events and the trajectory of pond
water balance are important considerations for interpreting pond chemical
concentration data for the purpose of inferring landscape-level changes to
permafrost environments.</p>
</sec>

      
      </body>
    <back><notes notes-type="dataavailability">

      <p id="d1e6469">Unprocessed data (not subject to temporal or spatial deviation
normalization) from all chemical analyses are available in the Supplement, Table S2.</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e6472"><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="https://doi.org/10.5194/bg-14-5471-2017-supplement" xlink:title="pdf">https://doi.org/10.5194/bg-14-5471-2017-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><notes notes-type="authorcontribution">

      <p id="d1e6478">MQM, RMP, MLM, and LAF designed the
sampling strategy and study objectives; LAF supervised the field
sample collection; MQM performed the laboratory analyses, analysed
the data, generated the figures, and prepared the manuscript; and RMP
and MLM provided comments on the manuscript composition and figure
presentation.</p>
  </notes><notes notes-type="competinginterests">

      <p id="d1e6484">The authors declare that they have no conflict of interest.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e6490">The funding for this research came from NSERC Discovery Grants
(Merrin L. Macrae, Richard M. Petrone), NSERC Northern Supplement
(Richard M. Petrone), the Northern Scientific Training Program, and Northern
Research Fund (Churchill Northern Studies Centre). Field assistance with
sample collection was provided by Matt Webb and Kimberly Thompson. Laboratory
assistance was provided by Vito Lam. Additional logistical support was
provided by the staff and volunteers of the Churchill Northern Studies
Centre. The authors thank Genevieve Ali and Janina Plach for helpful
discussions on statistical analyses of the data, the editorial team of
<italic>Biogeosciences</italic> led by Helge Niemann, and Maciej Bartosiewicz and the
anonymous referee for their helpful comments and insight towards improving
the final draft of the manuscript.<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?> Edited by:
Helge Niemann<?xmltex \hack{\newline}?> Reviewed by: Maciej Bartosiewicz and one
anonymous referee</p></ack><ref-list>
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    <!--<article-title-html>Capturing temporal and spatial variability in the chemistry of shallow permafrost ponds</article-title-html>
<abstract-html><p class="p">Across the circumpolar north, the fate of small freshwater ponds and lakes
( &lt;  1 km<sup>2</sup>) has been the subject of scientific interest due to their
ubiquity in the landscape, capacity to exchange carbon and energy with the
atmosphere, and their potential to inform researchers about past climates
through sediment records. A changing climate has implications for the
capacity of ponds and lakes to support organisms and store carbon, which in
turn has important feedbacks to climate change. Thus, an improved
understanding of pond biogeochemistry is needed. To characterize spatial and
temporal patterns in water column chemistry, a suite of tundra ponds were
examined to answer the following research questions:
(1) does temporal variability exceed spatial variability? (2) If temporal
variability exists, do all ponds (or groups of ponds) behave in a similar
temporal pattern, linked to seasonal hydrologic drivers or precipitation
events? Six shallow ponds located in the Hudson Bay Lowlands region were
monitored between May and October 2015 (inclusive, spanning the entire
open-water period). The ponds span a range of biophysical conditions
including pond area, perimeter, depth, and shoreline development. Water
samples were collected regularly, both bimonthly over the ice-free season and
intensively during and following a large summer storm event. Samples were
analysed for nitrogen speciation (NO<sub>3</sub><sup>−</sup>, NH<sub>4</sub><sup>+</sup>, dissolved
organic nitrogen) and major ions (Cl<sup>−</sup>, SO<sub>4</sub><sup>2−</sup>, K<sup>+</sup>,
Ca<sup>2+</sup>, Mg<sup>2+</sup>, Na<sup>+</sup>). Across all ponds, temporal variability
(across the season and within a single rain event) exceeded spatial
variability (variation among ponds) in concentrations of several major
species (Cl<sup>−</sup>, SO<sub>4</sub><sup>2−</sup>, K<sup>+</sup>, Ca<sup>2+</sup>, Na<sup>+</sup>).
Evapoconcentration and dilution of pond water with precipitation and runoff
inputs were the dominant processes influencing a set of chemical species
which are hydrologically driven (Cl<sup>−</sup>, Na<sup>+</sup>, K<sup>+</sup>, Mg<sup>2+</sup>,
dissolved organic nitrogen), whereas the dissolved inorganic nitrogen species
were likely mediated by processes within ponds. This work demonstrates the
importance of understanding hydrologically driven chemodynamics in permafrost
ponds on multiple scales (seasonal and event scale).</p></abstract-html>
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