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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 GmbH</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>

    <article-meta>
      <article-id pub-id-type="doi">10.5194/bg-12-3725-2015</article-id><title-group><article-title>Patterns and persistence of hydrologic carbon and nutrient export from
collapsing upland permafrost</article-title>
      </title-group><?xmltex \runningtitle{Patterns and persistence of hydrologic carbon and nutrient export}?><?xmltex \runningauthor{B. W. Abbott et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1 aff2">
          <name><surname>Abbott</surname><given-names>B. W.</given-names></name>
          <email>benabbo@gmail.com</email>
        <ext-link>https://orcid.org/0000-0001-5861-3481</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Jones</surname><given-names>J. B.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff3">
          <name><surname>Godsey</surname><given-names>S. E.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Larouche</surname><given-names>J. R.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff4">
          <name><surname>Bowden</surname><given-names>W. B.</given-names></name>
          
        </contrib>
        <aff id="aff1"><label>1</label><institution>Department of Biology and Wildlife and Institute of Arctic
Biology, University of Alaska Fairbanks, Fairbanks, USA</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Observatoire des Sciences de l'Univers de Rennes (OSUR), UMR6553 ECOBIO-CNRS, University of Rennes 1, <?xmltex \hack{\newline}?>Rennes, France</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>Department of Geosciences, Idaho State University,
Pocatello, USA</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>The Rubenstein School of Environment and Natural
Resources, University of Vermont, Birmingham, USA</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">B. W. Abbott (benabbo@gmail.com)</corresp></author-notes><pub-date><day>17</day><month>June</month><year>2015</year></pub-date>
      
      <volume>12</volume>
      <issue>12</issue>
      <fpage>3725</fpage><lpage>3740</lpage>
      <history>
        <date date-type="received"><day>1</day><month>January</month><year>2015</year></date>
           <date date-type="rev-request"><day>2</day><month>February</month><year>2015</year></date>
           <date date-type="rev-recd"><day>8</day><month>May</month><year>2015</year></date>
           <date date-type="accepted"><day>28</day><month>May</month><year>2015</year></date>
      </history>
      <permissions>
<license license-type="open-access">
<license-p>This work is licensed under a Creative Commons Attribution 3.0 Unported License. To view a copy of this license, visit <ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/3.0/">http://creativecommons.org/licenses/by/3.0/</ext-link></license-p>
</license>
</permissions><self-uri xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015.html">This article is available from https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015.html</self-uri>
<self-uri xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015.pdf">The full text article is available as a PDF file from https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015.pdf</self-uri>


      <abstract>
    <p>As high latitudes warm, vast stocks of carbon and nitrogen stored in
permafrost will become available for transport to aquatic ecosystems. While
there is a growing understanding of the potential effects of permafrost
collapse (thermokarst) on aquatic biogeochemical cycles, neither the spatial
extent nor temporal duration of these effects is known. To test hypotheses
concerning patterns and persistence of elemental export from upland
thermokarst, we sampled hydrologic outflow from 83 thermokarst features in
various stages of development across the North Slope of Alaska. We
hypothesized that an initial pulse of carbon and nutrients would be followed
by a period of elemental retention during feature recovery, and that the
duration of these stages would depend on feature morphology. Thermokarst
caused substantial increases in dissolved organic carbon and other solute
concentrations with a particularly large impact on inorganic nitrogen.
Magnitude and duration of thermokarst effects on water chemistry differed by
feature type and secondarily by landscape age. Most solutes returned to
undisturbed concentrations after feature stabilization, but elevated
dissolved carbon, inorganic nitrogen, and sulfate concentrations persisted
through stabilization for some feature types, suggesting that aquatic
disturbance by thermokarst for these solutes is long-lived. Dissolved
methane decreased by 90 % for most feature types, potentially due to high
concentrations of sulfate and inorganic nitrogen. Spatial patterns of carbon
and nutrient export from thermokarst suggest that upland thermokarst may be
a dominant linkage transferring carbon and nutrients from terrestrial to
aquatic ecosystems as the Arctic warms.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p>Arctic tundra and boreal forest have accumulated a vast pool of organic
carbon, twice as large as the atmospheric carbon pool and three times as
large as the carbon contained by all living things (Schuur et al., 2015;
Hugelius et al., 2014; Tarnocai et al., 2009). Climate change is
simultaneously causing widespread permafrost degradation (Slater and
Lawrence, 2013) and altering high-latitude hydrology (Peterson et al., 2006;
Rawlins et al., 2010), exposing carbon and other elements previously
protected in permafrost to transport and processing in Arctic rivers, lakes,
and estuaries. Fluxes of dissolved organic carbon (DOC), nutrients, and
other ions are changing across the permafrost region, and the rate of change
is projected to accelerate (Frey and McClelland, 2009; Jones et al., 2005;
Laudon et al., 2012; McClelland et al., 2007, 2014;
O'Donnell et al., 2012; Petrone et al., 2006; Rawlins et al., 2010; Striegl
et al., 2005; Tank et al., 2012). The interaction between changing hydrology
and degrading permafrost is one of the key uncertainties in predicting the
response of aquatic ecosystems to high-latitude climate change (Abbott et
al., 2015; Koch et al., 2013b; McClelland et al., 2008; Rawlins et al.,
2010; Vonk and Gustafsson, 2013).</p>
      <p>Permafrost degradation follows two basic trajectories. In permafrost with
little ground ice, the soil profile can thaw from the top down without
disturbing the surface, gradually exposing organic matter and solutes to
hydrologic export as the seasonally thawed active layer deepens (Koch et
al., 2013a; Petrone et al., 2006; Striegl et al., 2005). Alternatively, in
permafrost where ground ice volume exceeds soil pore space, thaw may cause
surface subsidence or collapse, termed thermokarst (Fig. 1; Kokelj and
Jorgenson, 2013). When thermokarst occurs on hillslopes it can abruptly
mobilize sediment, organic matter, and solutes from meters below the
surface, impacting kilometers of stream reach or entire lakes (Bowden et
al., 2008; Kokelj et al., 2005, 2013; Vonk et al., 2012).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1"><caption><p>The three most common thermokarst morphologies in upland tundra:
retrogressive thaw slumps (panels <bold>a</bold>, <bold>b</bold>), active-layer detachment slides
(<bold>c</bold>, <bold>d</bold>), and thermo-erosion gullies (<bold>e</bold>, <bold>f</bold>). Photo in panel <bold>(c)</bold> by A. W. Balser.</p></caption>
        <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f01.jpg"/>

      </fig>

      <p>The term thermokarst includes a suite of thermo-erosional features with
different morphologies determined primarily by ice content, substrate type,
landscape position, and slope (Osterkamp et al., 2009). In upland
landscapes, the three most common thermokarst morphologies are retrogressive
thaw slumps, active-layer detachment slides, and thermo-erosion gullies
(Fig. 1; Jorgenson and Osterkamp, 2005; Kokelj and Jorgenson, 2013; Krieger,
2012). Retrogressive thaw slumps (hereafter slumps) often form on
lakeshores, have a retreating headwall, and can be caused by a variety of
ground ice types including glacial ice, ice wedges, and cave ice.
Active-layer detachment slides (hereafter slides) form when the seasonally
thawed surface layer of vegetation and soil slips downhill over an ice-rich
transition zone (Lewkowicz, 2007). Thermo-erosion gullies (hereafter
gullies) form due to melting of ice wedges, growing with a generally linear
or dendritic pattern, and are often associated with water tracks or
headwater streams. These three morphologies currently impact ca. 1.5 % of
the landscape in the western foothills of the Brooks Range (Krieger, 2012)
and could affect 20–50 % of uplands in the continuous permafrost region
by the end of the century based on projected thaw and estimates of ground
ice distribution (Slater and Lawrence, 2013; Zhang et al., 2000), though
circum-Arctic prevalence and development of upland thermokarst are poorly
constrained (Jorgenson et al., 2006; Lantz and Kokelj, 2008; Yoshikawa et
al., 2002).</p>
      <p>Upland thermokarst can alter the age and degradability of organic carbon,
releasing older particulate organic carbon (Lafreniere and Lamoureux, 2013)
and more labile DOC during formation (Abbott et al., 2014; Cory et al.,
2013; Vonk et al., 2013). Mineral soil exposed by thermokarst can increase
solutes available for hydrologic transport (Harms et al., 2013; Kokelj and
Burn, 2003; Kokelj et al., 2013; Louiseize et al., 2014), but it can also
adsorb DOC, reducing concentration in feature outflows and receiving waters,
resulting in greater water clarity after sediment loading and settling
(Kokelj et al., 2005; Thompson et al., 2012). These changes in sediment
delivery, light penetration, and nutrients can alter aquatic food webs in
receiving ecosystems (Mesquita et al., 2010; Thienpont et al., 2013;
Thompson et al., 2012).</p>
      <p>Despite a growing understanding of the potential effects of upland
thermokarst on aquatic biogeochemical cycles, there is conflicting evidence
on the temporal duration of these effects and their overall importance to
ecological functioning, precluding conceptualization of patterns of
thermokarst impacts and their incorporation into coupled climate models. If
thermokarst disturbance is hydrologically connected to aquatic ecosystems,
substantial loading of sediment, carbon, and nutrients can occur (Bowden et
al., 2008; Kokelj et al., 2005, 2013; Shirokova et al., 2013;
Thienpont et al., 2013; Vonk et al., 2013), though not all features
connected to surface waters result in enhanced carbon and nutrient export
(Thompson et al., 2012). Conversely, if thermokarst is hydrologically
isolated from surface waters, such as when failures occur high on
hillslopes, even dramatic disturbance can have little or no impact on
aquatic chemistry and elemental budgets (Lafreniere and Lamoureux, 2013;
Lewis et al., 2012). The duration of carbon and nutrient release, and the
persistence of biogeochemical disturbance in affected ecosystems after
feature stabilization is largely unknown, with altered surface water
chemistry lasting for decades in some cases of nutrient loading or surface
disturbance (Kokelj et al., 2005; Thienpont et al., 2013), or fading after
less than a year in others (Lafreniere and Lamoureux, 2013).</p>
      <p>To address these knowledge gaps, we sampled surface outflow from thermokarst
features in various stages of development across a broad portion of the
North Slope of Alaska. We focused on two questions. First, how does
thermokarst formation alter hydrologic release of carbon and nutrients, and
second, can the type and duration of hydrologic release be predicted based
on feature morphology or landscape characteristics? We hypothesized that
upland thermokarst would initially stimulate nutrient release due to
disruption of soil aggregates, accelerated organic matter mineralization in
impacted soils, decreased plant uptake, and direct release from melting
ground ice. However, following nutrient retention theory (Vitousek and
Reiners, 1975), we hypothesized that this pulse of nutrients would be
followed by a period of elemental retention due to enhanced nutrient uptake
by recovering vegetation and diminished pools of organic matter and
nutrients following disturbance. We hypothesized that DOC export would
depend on the balance between DOC production from soil disruption and DOC
removal via adsorption by exposed mineral soil as well as enhanced
processing of DOC within features due to abundant nutrients and
biodegradable DOC from permafrost. In regards to feature morphology, we
hypothesized that fundamental differences in formation and functioning of
slides, gullies, and slumps, such as the amount of organic and mineral soil
displaced, type of ground ice, location on the landscape, and duration of
disturbance, would result in systematic differences in carbon and nutrient
release. We predicted that slumps would have the largest and longest impact,
slides would have a large but short-lived impact, and gullies would have a
muted impact of intermediate duration.</p>
</sec>
<sec id="Ch1.S2">
  <title>Methods</title>
<sec id="Ch1.S2.SS1">
  <title>Study sites</title>
      <p>We tested our hypotheses about thermokarst carbon and nutrient export with
observations from 83 slides, gullies, and slumps on the North Slope of
Alaska (Fig. 2). Features were identified by aerial surveys, satellite
imagery, and previous studies (Abbott et al., 2014; Bowden et al., 2008;
Gooseff et al., 2009) and were located in three areas of upland tundra
underlain by continuous permafrost in the foothills of the Brooks Range. We
collected samples during the growing season (June–August) of 2009–2012 and
May of 2011 in the region surrounding the Toolik Field Station, with
additional sampling in the Noatak National Preserve near the Kelly River
Ranger Station in 2010 and Feniak Lake in 2011. Most sites were sampled a
single time over the course of the study, except for the five most
accessible features near the Toolik Field Station, which we sampled 2–4
times each summer from 2009 to 2011.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><caption><p>Map of study area. Features near the Kelly River Ranger Station
were sampled in July of 2010, near Feniak Lake field camp in July of 2011,
and near the Toolik Field Station in the summers of 2009–2012.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f02.png"/>

        </fig>

      <p>The Toolik Field Station is located 254 km north of the Arctic Circle and
180 km south of the Arctic Ocean. The mean annual temperature is
<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>10 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, with mean monthly temperatures ranging from <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>25 in January to 11.5 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C in July. The region receives 320 mm of
precipitation annually, with 200 mm falling between June and August (Toolik
Environmental Data Center Team, 2014). Feniak Lake is located 360 km west of
the Toolik Field Station in the central Brooks Range at the northeast
boarder of the Noatak National Preserve. The mean annual temperature is
<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>7 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C (Jorgenson et al., 2008) and mean precipitation is 450 mm
(WRCC, 2011). The Kelly River Ranger Station is located on the western
boarder of the Noatak National Preserve, 170 km west of Feniak Lake. Average
annual temperature is <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>5.4 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and the area receives a mean of
300 mm of precipitation, a third of which falls during the growing season
(Stottlemyer, 2001).</p>
      <p>Vegetation is typical of Arctic tundra across the study region and includes
moist acid tundra characterized by the tussock-forming sedge <italic>Eriophorum vaginatum</italic>, moist
nonacidic tundra, and shrub tundra (Bhatt et al., 2010; Walker et al.,
1998), with isolated stands of white spruce (<italic>Picea glauca</italic>) near the Kelly River Ranger
Station (Sullivan and Sveinbjornsson, 2010). All three areas occur in
bioclimate subzone E, the warmest region in the continuous permafrost zone
(Walker et al., 2010). The foothills of the Brooks Range have been affected
by multiple glaciations starting in the late Tertiary and continuing to 11 kyr BP (Hamilton, 2003). Repeated rounds of glacial advance and retreat
have resulted in a patchwork of glacial till, bedrock, and loess parent
materials of various ages (Hamilton, 2010). Time since last glaciation can
be associated with ecosystem properties including pH, organic layer depth,
nutrient pools, vegetation community, and biogeochemical rates (Epstein et
al., 2004; Hobbie et al., 2002; Lee et al., 2011; Walker et al., 1998).</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Experimental design and sampling</title>
      <p>To test our hypotheses concerning the intensity and duration of thermokarst
impacts on aquatic chemistry, we sampled thermokarst features in all stages
of development across landscape ages and vegetation types. We collected
water from 83 thermokarst outflows and 61 adjacent undisturbed water bodies
such as water tracks and first-order streams (22 locations did not have a
suitable paired reference site). To quantify the evolution and duration of
thermokarst effects through time, we classified features on a 0–3 index
(Fig. 3) following the development of a hypothetical feature from before
initiation (0) to after stabilization (3). Development stages were defined
as follows: (0) no apparent present or past thermo-degradation, (1) active
thermo-degradation (&gt; 25 % of headwall is actively expanding)
with completely turbid outflow, (2) moderate thermo-degradation (&lt; 25 % of headwall is expanding) with somewhat turbid outflow, and (3)
stabilized or limited thermo-degradation with complete or partial
revegetation and clear outflow. Ideally we would have tested for trends in
elemental export based on absolute feature age rather than a development
stage proxy. However, identifying a reliable time since formation requires
high-resolution remote sensing or radiocarbon dating (Krieger, 2012; Balser
and Jones, 2014; Pizano et al., 2014), which was beyond the scope of our study
given the large number of features sampled. Features were classified in the
field prior to any chemical analyses, precluding the possibility of bias in
classification based on chemical signature. We also performed a sensitivity
analysis, randomly excluding a third of the thermokarst features, to explore
robustness of the classification, which did not substantively change the
results or interpretation.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><caption><p>Aerial view of thaw slumps in various development stages.
Samples were collected from feature outflows and adjacent water bodies such
as unimpacted water tracks, streams, and lakes to assess the impact of
thermokarst on water chemistry.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f03.png"/>

        </fig>

      <p>Vegetation class was determined in the field and cross-referenced with
published vegetation maps when available (Walker et al., 2005). Glacial
geology and surface age were based on recent maps of the study region
(Hamilton, 2010, 2003; Kanevskiy et al., 2011). Most site ages ranged from
10 to 200 kyr, though six sites occurred on surfaces unglaciated for more than
1000 kyr. We classified sites on surfaces younger than 25 kyr as young, and
sites over 50 kyr as old, corresponding to the split between the Itkillik I
and II advances (Hamilton, 2003).</p>
      <p>Samples for carbon and nutrient analysis were filtered in the field (0.7 <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>m effective pore size, Advantec GF-75) into 60 mL high-density
polyethylene (HDPE) bottles, except when excess sediment required settling
overnight when samples were filtered within 24 h. After filtration,
samples were frozen until analysis. We measured DOC and dissolved inorganic
carbon (DIC) with a Shimadzu TOC-5000 connected to an Antek 7050
chemiluminescent detector to quantify total dissolved nitrogen after
combustion to NO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula>. We analyzed major ions (NO<inline-formula><mml:math 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>,
NO<inline-formula><mml:math display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:msubsup></mml:mrow></mml:math></inline-formula>, SO<inline-formula><mml:math 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>, Cl<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, NH<inline-formula><mml:math 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>, Ca<inline-formula><mml:math 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 display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, Mg<inline-formula><mml:math 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 display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> on a Dionex DX-320 ion chromatograph. We
calculated dissolved organic nitrogen (DON) by subtracting dissolved
inorganic nitrogen (DIN <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> NO<inline-formula><mml:math 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> NH<inline-formula><mml:math 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> NO<inline-formula><mml:math display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn><mml:mo>-</mml:mo></mml:msubsup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> from total dissolved nitrogen, and we calculated the DOC to
DON ratio (C : N) of dissolved organic matter, an indicator of organic matter
source and degree of prior processing (Amon et al., 2012). To determine the
percentage of thermokarst outflow coming from ground ice, we analyzed
<inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="italic">δ</mml:mi><mml:mi>D</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O on a Picarro L1102-i via cavity ring-down
spectroscopy.</p>
      <p>Because lateral fluxes of dissolved gas can constitute a considerable
portion of Arctic carbon budgets (Kling et al., 1992; Striegl et al., 2012),
we measured dissolved CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, and N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O in feature outflows
and reference water. At each site we collected a 30 mL sample of bubble-free
water in a 60 mL gas-tight syringe accompanied by an ambient atmospheric
sample in a 15 mL evacuated gas vial. Upon return to the lab or camp we
added 30 mL of atmosphere to the syringe and shook vigorously for 2 min to facilitate equilibration of dissolved gases with the introduced
headspace, and then injected a sample of the headspace into an evacuated gas
vial for storage until analysis. We determined CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, and
N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentration of the headspace sample on a Varian 3300 gas
chromatograph with a flame ionization detector and methanizer for carbon
species and an electron capture detector for N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O. We calculated the
proportion of total gas dissolved in solution and in the headspace using
Henry's constants adjusted for extraction temperature (Wilhelm et al.,
1977), and subtracted ambient gas introduced during extraction to determine
initial concentration. We calculated saturation as the percent of
equilibrium water concentration based on atmospheric partial pressure and
water temperatures at the time of sampling and extraction.</p>
      <p>To determine the direct contribution of carbon and nutrients from ground
ice, we sampled exposed headwall ice at 24 sites. Because gravel and cobbles
prevented motorized coring, we collected ice scrapings with a hand corer
into Ziploc<sup>™</sup> bags, which we filtered and analyzed after melt
as previously described. We compared concentrations of carbon and nutrients
in ground ice to feature outflows to determine whether solute concentrations
were changing as water flowed through the feature. At these sites we used
the difference between the <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O of ground ice and adjacent
reference water (stream or water track) to determine the proportion of
outflow contributed by ground ice. We calculated the proportion from ground
ice with a simple two-end-member model:</p>
      <p><disp-formula id="Ch1.E1" content-type="numbered"><mml:math display="block"><mml:mrow><?xmltex \hack{\hbox\bgroup\fontsize{8}{8}\selectfont$\displaystyle}?><mml:mtext mathvariant="normal">Ground ice proportion</mml:mtext><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mtext>out</mml:mtext></mml:msub><mml:mo>-</mml:mo><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mtext>sw</mml:mtext></mml:msub><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mtext>ice</mml:mtext></mml:msub><mml:mo>-</mml:mo><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mtext>sw</mml:mtext></mml:msub><mml:mo>)</mml:mo><mml:mo>,</mml:mo><?xmltex \hack{$\egroup}?></mml:mrow></mml:math></disp-formula>

          where out is feature outflow, sw is undisturbed surface water, and ice is
headwall ice.</p>
      <p>To convert carbon and nitrogen concentrations into elemental loads and areal
yields we measured discharge at the outflow of 26 thermokarst features using
salt-dilution gauging (Figs. 1 and 3). We logged electrical conductivity
with a YSI Professional Plus conductivity meter and added 10–100 g of
dissolved NaCl upstream of the probe by 10–20 m, depending on the size of
the outflow. Discharge was determined by total dilution of the tracer as it
passed by the probe (Wlostowski et al., 2013). We mapped feature perimeters
with a commercial-grade, handheld GPS, except for four sites around Toolik,
which were mapped by the Toolik Field Station GIS staff with a survey-grade
GPS and base station. We determined areal DOC and DIN daily yields from the
gauged sites by multiplying outflow concentration by discharge and dividing
by the area of the feature. For sites with surface water flowing into the
top of the feature (primarily gullies but also some slides and slumps) we
subtracted the reference concentration of each solute before calculating
yield, so the estimate represented only the contribution from the area
disturbed by thermokarst (assuming that any unmeasured lateral water inputs
along the feature margin have the same carbon and nitrogen concentrations).
Because determining contributing area for reference sites was not possible
due to the low resolution of digital elevation models for the study region,
we compared yields from thermokarst features to published yields of DOC and
DIN from upland Arctic tundra (Giesler et al., 2014; McClelland et al.,
2007, 2014; Olefeldt et al., 2013; Peterson et al., 1993, 1986; Townsend-Small et al., 2011).</p>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Statistical analyses</title>
      <p>We used a linear mixed-effects model to test for effects of thermokarst
development stage, feature type, vegetation, and landscape age on water
chemistry while accounting for spatial and temporal nonindependence in the
data. For each water chemistry parameter we used a mixed-effects analysis of
variance (ANOVA) with development stage crossed with feature type and
vegetation and landscape age as fixed effects. We included site as a random
effect to pair thermokarst outflows with their adjacent reference water. The
models included seasonal and interannual variability both across and within
sites. We visually inspected residual plots for deviations from normality
and homoscedasticity, and transformed response and predictor variables when
necessary. We simplified the full model by automated backwards elimination,
using restricted maximum likelihood to evaluate fixed effects and likelihood
ratio tests for random effects. To test for differences between groups, we
performed post hoc Tukey honest significant difference tests on the least-squares means using Satterthwaite approximation to estimate denominator
degrees of freedom. We used Pearson product-moment correlation to test for
associations between water chemistry parameters and development stage, which
we recoded low to high and treated as a continuous variable of disturbance
intensity. A decision criterion of <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> 0.05 was used for all
tests.</p>
      <p>All analyses were performed in R 3.0.2 (R Core Team, 2013) with the lme4 and
lmerTest packages (Bates et al., 2013; Kuznetsova et al., 2014). The
complete data set is available through the Advanced Cooperative Arctic Data
and Information Service at <uri>www.aoncadis.org/dataset/soil_water_gas_alaskan_thermokarst.html</uri>.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results</title>
<sec id="Ch1.S3.SS1">
  <title>Thermokarst distribution and characteristics</title>
      <p>Feature types were not distributed equally among vegetation classes, with
most active-layer detachment slides occurring on nonacidic tundra, most
thermo-erosion gullies occurring on acidic tundra, and thaw slumps
distributed among tundra types (Table 1). Feature types were also unevenly
distributed between development stages, with over half of slumps classified
as stage 1 (very active) compared to approximately 30 % of slides and
gullies. Over 90 % of all features were associated with or intersected a
water body (Table 1). Slides and gullies occurred primarily on or next to
water tracks or headwater streams and the majority of thaw slumps were on
lakeshores. Slides tended to occur in the highest topographic positions,
slumps were distributed across high- and low-gradient surfaces, and gullies
were most common on foot slopes or valley bottoms.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p>Characteristics of upland thermokarst features in study.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="center"/>
     <oasis:colspec colnum="3" colname="col3" align="center"/>
     <oasis:colspec colnum="4" colname="col4" align="center"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Active layer</oasis:entry>  
         <oasis:entry colname="col3">Thermo-</oasis:entry>  
         <oasis:entry colname="col4">Retrogressive</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">detachment slide</oasis:entry>  
         <oasis:entry colname="col3">erosion gully</oasis:entry>  
         <oasis:entry colname="col4">thaw slump</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Outflow discharge (L s<inline-formula><mml:math 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="col2">2.8 (1.1)</oasis:entry>  
         <oasis:entry colname="col3">1.4 (0.4)</oasis:entry>  
         <oasis:entry colname="col4">0.95 (0.3)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Percent of outflow from ground ice</oasis:entry>  
         <oasis:entry colname="col2">8.6 (5.5)</oasis:entry>  
         <oasis:entry colname="col3">37 (32)</oasis:entry>  
         <oasis:entry colname="col4">49 (7.6)</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"><inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi>n</mml:mi><mml:mo>*</mml:mo></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">7</oasis:entry>  
         <oasis:entry colname="col3">3</oasis:entry>  
         <oasis:entry colname="col4">16</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Percent of features</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">intersecting river/stream/water track</oasis:entry>  
         <oasis:entry colname="col2">92</oasis:entry>  
         <oasis:entry colname="col3">56</oasis:entry>  
         <oasis:entry colname="col4">40</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">flowing into lake</oasis:entry>  
         <oasis:entry colname="col2">0</oasis:entry>  
         <oasis:entry colname="col3">38</oasis:entry>  
         <oasis:entry colname="col4">58</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">unassociated with water body</oasis:entry>  
         <oasis:entry colname="col2">8</oasis:entry>  
         <oasis:entry colname="col3">6</oasis:entry>  
         <oasis:entry colname="col4">2</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Percent of features occurring on</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">moist acidic tundra</oasis:entry>  
         <oasis:entry colname="col2">13</oasis:entry>  
         <oasis:entry colname="col3">53</oasis:entry>  
         <oasis:entry colname="col4">22</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">moist nonacidic tundra</oasis:entry>  
         <oasis:entry colname="col2">64</oasis:entry>  
         <oasis:entry colname="col3">5</oasis:entry>  
         <oasis:entry colname="col4">45</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">shrub tundra</oasis:entry>  
         <oasis:entry colname="col2">23</oasis:entry>  
         <oasis:entry colname="col3">42</oasis:entry>  
         <oasis:entry colname="col4">33</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Percent of features in development stage</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">1</oasis:entry>  
         <oasis:entry colname="col2">28</oasis:entry>  
         <oasis:entry colname="col3">32</oasis:entry>  
         <oasis:entry colname="col4">57</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">2</oasis:entry>  
         <oasis:entry colname="col2">36</oasis:entry>  
         <oasis:entry colname="col3">42</oasis:entry>  
         <oasis:entry colname="col4">17</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">3</oasis:entry>  
         <oasis:entry colname="col2">36</oasis:entry>  
         <oasis:entry colname="col3">26</oasis:entry>  
         <oasis:entry colname="col4">26</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi>n</mml:mi><mml:mrow><mml:mo>*</mml:mo><mml:mo>*</mml:mo></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">22</oasis:entry>  
         <oasis:entry colname="col3">34</oasis:entry>  
         <oasis:entry colname="col4">27</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p>Mean (SE) characteristics of upland thermokarst on the North Slope of
Alaska. <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula> Sample size for discharge and ground ice contribution
measurements.
<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>*</mml:mo><mml:mo>*</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula> Sample size for landscape position and development stage. Development
stages were defined as follows: (0) no apparent present or past
thermo-degradation, (1) active thermo-degradation (&gt; 25 % of
headwall is actively expanding) with completely turbid outflow, (2) moderate
thermo-degradation (&lt; 25 % of headwall is expanding) with
somewhat turbid outflow, and (3) stabilized or limited thermo-degradation with
complete or partial revegetation and clear outflow.</p></table-wrap-foot></table-wrap>

      <p>Discharge from thermokarst features varied widely by feature type and
individual features in the study, from no flow at some stabilized slumps and
slides to 9.4 L s<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> at one slide (Table 1). Mean discharge was
highest for slides and lowest for slumps. For sites where we estimated the
proportion of outflow derived from ground ice, the ice contribution varied
from 0 to 97 %. Slumps had the highest average ground ice contribution and
slides had the lowest, though these values are not representative of all
features, since they are only based on sites with exposed ground ice.
Generally sites with high discharge (&gt; 2 L s<inline-formula><mml:math 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> had little
contribution from ground ice, except several large slumps with very active
headwall retreat.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><caption><p>Correlations between water chemistry parameters for 83 thermokarst features and 61 reference water tracks and first order streams.</p></caption><oasis:table frame="topbot"><?xmltex \begin{scaleboxenv}{.85}[.85]?><oasis:tgroup cols="16">
     <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:colspec colnum="10" colname="col10" align="right"/>
     <oasis:colspec colnum="11" colname="col11" align="right"/>
     <oasis:colspec colnum="12" colname="col12" align="right"/>
     <oasis:colspec colnum="13" colname="col13" align="right"/>
     <oasis:colspec colnum="14" colname="col14" align="right"/>
     <oasis:colspec colnum="15" colname="col15" align="right"/>
     <oasis:colspec colnum="16" colname="col16" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Activity</oasis:entry>  
         <oasis:entry colname="col3">DOC</oasis:entry>  
         <oasis:entry colname="col4">DON</oasis:entry>  
         <oasis:entry colname="col5">DOC : DON</oasis:entry>  
         <oasis:entry colname="col6">CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col7">CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col8">DIC</oasis:entry>  
         <oasis:entry colname="col9">NH<inline-formula><mml:math 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="col10">NO<inline-formula><mml:math 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="col11">N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O</oasis:entry>  
         <oasis:entry colname="col12">SO<inline-formula><mml:math 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="col13">Ca<inline-formula><mml:math 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="col14">Mg<inline-formula><mml:math 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="col15">K<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col16">Na<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">ln(DOC)</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.34</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:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ln(DON)</oasis:entry>  
         <oasis:entry colname="col2"><bold>0.45</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.94</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:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ln(DOC : DON)</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.43</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.15</bold></oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.46</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:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ln(CO<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.08</oasis:entry>  
         <oasis:entry colname="col3"><bold>0.27</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.23</bold></oasis:entry>  
         <oasis:entry colname="col5">0.13</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:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ln(CH<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.13</oasis:entry>  
         <oasis:entry colname="col3"><bold>0.18</bold></oasis:entry>  
         <oasis:entry colname="col4">0.09</oasis:entry>  
         <oasis:entry colname="col5"><bold>0.25</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.59</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:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">DIC<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mn>0.5</mml:mn></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.25</bold></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.10</oasis:entry>  
         <oasis:entry colname="col4">0.03</oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.35</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.22</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.43</bold></oasis:entry>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NH<inline-formula><mml:math display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">4</mml:mn><mml:mrow><mml:mo>+</mml:mo><mml:mo>(</mml:mo><mml:mn>0.25</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.52</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.57</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.59</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.30</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.16</bold></oasis:entry>  
         <oasis:entry colname="col7">0.05</oasis:entry>  
         <oasis:entry colname="col8">0.08</oasis:entry>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NO<inline-formula><mml:math display="inline"><mml:mrow><mml:msubsup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn><mml:mrow><mml:mo>-</mml:mo><mml:mo>(</mml:mo><mml:mn>0.25</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.42</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.16</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.24</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.24</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.14</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.07</oasis:entry>  
         <oasis:entry colname="col8">0.00</oasis:entry>  
         <oasis:entry colname="col9"><bold>0.38</bold></oasis:entry>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>(</mml:mo><mml:mn>0.25</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">0.12</oasis:entry>  
         <oasis:entry colname="col3"><bold>0.38</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.38</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.06</oasis:entry>  
         <oasis:entry colname="col6">0.14</oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.02</oasis:entry>  
         <oasis:entry colname="col8">0.03</oasis:entry>  
         <oasis:entry colname="col9"><bold>0.42</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.39</bold></oasis:entry>  
         <oasis:entry colname="col11"/>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SO<inline-formula><mml:math 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:mo>(</mml:mo><mml:mn>0.25</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:msubsup></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.40</bold></oasis:entry>  
         <oasis:entry colname="col3">0.12</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.26</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.44</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.31</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.41</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.52</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.23</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.34</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.24</bold></oasis:entry>  
         <oasis:entry colname="col12"/>  
         <oasis:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ln(Ca<inline-formula><mml:math 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></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.43</bold></oasis:entry>  
         <oasis:entry colname="col3">0.07</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.25</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.52</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.24</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.39</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.67</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.18</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.34</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.20</bold></oasis:entry>  
         <oasis:entry colname="col12"><bold>0.79</bold></oasis:entry>  
         <oasis:entry colname="col13"/>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Mg<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>+</mml:mo><mml:mo>(</mml:mo><mml:mn>0.5</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.43</bold></oasis:entry>  
         <oasis:entry colname="col3">0.13</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.27</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.45</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.27</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.45</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.70</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.27</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.24</bold></oasis:entry>  
         <oasis:entry colname="col11">0.15</oasis:entry>  
         <oasis:entry colname="col12"><bold>0.83</bold></oasis:entry>  
         <oasis:entry colname="col13"><bold>0.84</bold></oasis:entry>  
         <oasis:entry colname="col14"/>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">K<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>+</mml:mo><mml:mo>(</mml:mo><mml:mn>0.25</mml:mn><mml:mo>)</mml:mo></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.42</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.30</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.39</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.35</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.22</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.23</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.15</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.42</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.32</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.21</bold></oasis:entry>  
         <oasis:entry colname="col12"><bold>0.48</bold></oasis:entry>  
         <oasis:entry colname="col13"><bold>0.39</bold></oasis:entry>  
         <oasis:entry colname="col14"><bold>0.34</bold></oasis:entry>  
         <oasis:entry colname="col15"/>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ln(Na<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.47</bold></oasis:entry>  
         <oasis:entry colname="col3">0.02</oasis:entry>  
         <oasis:entry colname="col4"><bold>0.18</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.45</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.37</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.50</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.57</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.15</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.29</bold></oasis:entry>  
         <oasis:entry colname="col11">0.07</oasis:entry>  
         <oasis:entry colname="col12"><bold>0.72</bold></oasis:entry>  
         <oasis:entry colname="col13"><bold>0.69</bold></oasis:entry>  
         <oasis:entry colname="col14"><bold>0.73</bold></oasis:entry>  
         <oasis:entry colname="col15"><bold>0.48</bold></oasis:entry>  
         <oasis:entry colname="col16"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ln(Cl<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2"><bold>0.43</bold></oasis:entry>  
         <oasis:entry colname="col3"><bold>0.43</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.54</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.41</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.20</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo mathvariant="bold">-</mml:mo></mml:math></inline-formula><bold>0.25</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.21</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.47</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.43</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.27</bold></oasis:entry>  
         <oasis:entry colname="col12"><bold>0.48</bold></oasis:entry>  
         <oasis:entry colname="col13"><bold>0.37</bold></oasis:entry>  
         <oasis:entry colname="col14"><bold>0.35</bold></oasis:entry>  
         <oasis:entry colname="col15"><bold>0.63</bold></oasis:entry>  
         <oasis:entry colname="col16"><bold>0.42</bold></oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup><?xmltex \end{scaleboxenv}?></oasis:table><?xmltex \begin{scaleboxenv}{.85}[.85]?><table-wrap-foot><p>Strength of relationships was determined by Pearson product-moment
correlation. Significant correlations (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.05) are in bold.
Relationships were visually inspected and transformed when necessary to meet
the assumption of linearity (log and exponential transformations noted in
the variable column on the left). All units are <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>M except dissolved
gases (CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>, and N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O), which are ppmv; DOC : DON, which is
a unitless ratio; and activity, which is recoded development stage 1–4 (low
to high) treated as a nonparametric continuous variable.</p></table-wrap-foot><?xmltex \end{scaleboxenv}?></table-wrap>

<?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S3.SS2">
  <title>Effects of development stage and morphology on water chemistry</title>
      <p>Thermokarst significantly altered concentrations of carbon, nitrogen, and
other solutes, but the magnitude and duration of these effects differed by
feature type (Figs. 4, 5, and 6). For most parameters, effects were largest
at the most active features, with differences tapering off as activity
decreased. However, DOC in slide outflows as well as DIC, Mg<inline-formula><mml:math 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>,
Ca<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and dissolved N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O concentrations in gully outflows was
highest in stabilized features. Slumps tended to have the largest effect on
solute concentrations. For example, SO<inline-formula><mml:math 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> concentration was
30-fold higher than reference in stage-1 outflows, compared to 3.3- and
1.5-fold higher for gullies and slides, respectively. Gully reference and
outflow chemistry was generally distinct from slides and slumps, with higher
dissolved gas concentrations and DOC : DON, but lower concentrations of ions
and DIC.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p>Dissolved carbon species and characteristics in outflow from 22
active-layer detachment slides, 19 thermo-erosion gullies, 42 thaw slumps,
and 61 reference features in upland tundra on the North Slope of Alaska.
Open circles signify statistical difference from stage-0 undisturbed sites,
<inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> 0.05. Different letters above panels represent significant
differences between feature types. Error bars represent SE estimated by
mixed-effects ANOVA after accounting for between-site variability. See Table 1 for complete definition
of development stages: 0, reference; 1, most
active; and 3, stabilized. Note the log scale for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f04.pdf"/>

        </fig>

      <p>Thaw slumps caused the greatest increase in dissolved organic matter
concentration, with DOC and DON 2.6- and 4.0-fold greater in stage-1
features, compared with 1.6- and 1.4-fold increases in slides, and 2.2- and
1.6-fold increases in gullies of DOC and DON, respectively (Fig. 4).
Thermokarst had a much larger impact on inorganic nitrogen, with mean
NH<inline-formula><mml:math 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 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 9- to 27-fold greater in
stage-1 features (Fig. 5). Consequently, the relative proportion of DIN,
which made up less than 10 % of total nitrogen in reference waters,
constituted 26 to 38 % of total nitrogen in stage-1 features and 48 %
of total nitrogen in stage-2 gullies (Fig. 7). NH<inline-formula><mml:math 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> was the
dominant form of DIN for all feature types and development stages except
stage-3 (stabilized) slides, where NO<inline-formula><mml:math 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> made up 70 % of DIN.
Elevated DIN persisted through stage 2 for slumps and through stabilization
for gullies.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5"><caption><p>Nitrogen species and sulfate concentrations in outflow from 22
active-layer detachment slides, 19 thermo-erosion gullies, 42 thaw slumps,
and 61 reference features. See Table 1 for complete definition of
development stages: 0, reference; 1, most active; and 3, stabilized. Note
log scales for NO<inline-formula><mml:math 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 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>. Symbology the same as Fig. 2.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f05.pdf"/>

        </fig>

      <p>Dissolved CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> concentration was 92 and 89 % lower than
reference for stage-1 gullies and slumps, respectively (Fig. 4). However,
there were no significant differences by development stage for dissolved
CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, and dissolved N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O was only significantly elevated in
stabilized gullies. Across all development stages and feature types, 93
and 97 % of all samples were supersaturated with CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> and CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>,
respectively, whereas 51 % of samples were supersaturated with N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6"><caption><p>Major ion concentrations in outflow from 22 active-layer
detachment slides, 19 thermo-erosion gullies, 42 thaw slumps, and 61
reference features. See Table 1 for complete definition of development
stages: 0, reference; 1, most active; and 3, stabilized. Note log scales
for NO<inline-formula><mml:math 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 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>. Symbology the same as Fig. 2.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f06.pdf"/>

        </fig>

      <p>Specific yields of DOC and DIN from stage-1 thermokarst features were 30-
and 57-fold higher than literature values for undisturbed tundra,
respectively (Fig. 8). The geometric mean yield for level-1 features was
0.45 g C m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> day<inline-formula><mml:math 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> for DOC and 3.8 mg N m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> day<inline-formula><mml:math 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> for
DIN, though there was considerable variability between individual sites
within activity levels. DOC and DIN yields from stabilized features were
within the range of literature values for undisturbed tundra. Yields varied
more strongly by activity level than by feature type, with similar yields
from the most active ALDS, gullies, and slumps.</p>
      <p>For the five sites with repeated measures of thermokarst outflow chemistry,
solute concentrations were variable between samplings but did not show
systematic seasonal or interannual trends, except for DIC concentration and
<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O, which both increased through the growing season (Figs. S1–S8 in the Supplement).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7"><caption><p>The relative proportion of carbon and nitrogen species in
thermokarst outflow by feature type and development stage. See Figs. 2 and 3
for estimates of error and statistical tests for each parameter and Table 1
for complete definition of development stages: 0, reference; 1, most
active; and 3, stabilized.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f07.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8"><caption><p>Geometric mean (SE) of dissolved organic carbon and dissolved
inorganic nitrogen yield for thermokarst features in different development
stages. Yield was calculated by difference in concentration above and below thermokarst feature multiplied by
discharge and divided by feature area. Reference yields (stage 0) are
maximum, minimum, and mean estimates from the literature for Arctic tundra
(Giesler et al., 2014; McClelland et al., 2007; McClelland et al., 2014;
Olefeldt et al., 2013; Peterson et al., 1993; Peterson et al., 1986;
Townsend-Small et al., 2011). See Table 1 for complete definition of
development stages: 0, reference; 1, most active; and
3, stabilized.</p></caption>
          <?xmltex \igopts{width=227.622047pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f08.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS3">
  <title>Ground ice, vegetation, and landscape age</title>
      <p>Permafrost ice was high in dissolved carbon, nitrogen, and solutes and had a
depleted <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O signature relative to reference waters (Table 3).
Average concentrations of DIC, NH<inline-formula><mml:math 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 K<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> were higher in
ground ice than feature outflow, indicating uptake or dilution during
transport from the feature headwall to outflow. However, all other solutes,
notably DOC, NO<inline-formula><mml:math 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 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 higher in outflows
than in ground ice, indicating net production or contribution from soils or
more concentrated flow paths during transit.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T3" specific-use="star"><caption><p>Water chemistry for ground ice, thermokarst outflows, and reference waters.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <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:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Solute (<inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>M)*</oasis:entry>  
         <oasis:entry colname="col2">Ground ice</oasis:entry>  
         <oasis:entry colname="col3">Feature outflow</oasis:entry>  
         <oasis:entry colname="col4">Reference water</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">DOC</oasis:entry>  
         <oasis:entry colname="col2">1213 (413)</oasis:entry>  
         <oasis:entry colname="col3">2109 (349)</oasis:entry>  
         <oasis:entry colname="col4">821 (120)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">DOC : DON</oasis:entry>  
         <oasis:entry colname="col2">18.7 (2.0)</oasis:entry>  
         <oasis:entry colname="col3">27.1 (2.1)</oasis:entry>  
         <oasis:entry colname="col4">33.8 (2.0)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">DIC</oasis:entry>  
         <oasis:entry colname="col2">953 (156)</oasis:entry>  
         <oasis:entry colname="col3">893 (98)</oasis:entry>  
         <oasis:entry colname="col4">587 (156)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NH<inline-formula><mml:math 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">54.7 (11.2)</oasis:entry>  
         <oasis:entry colname="col3">42.5 (8.9)</oasis:entry>  
         <oasis:entry colname="col4">2.08 (0.65)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">NO<inline-formula><mml:math 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">2.68 (1.16)</oasis:entry>  
         <oasis:entry colname="col3">3.95 (0.92)</oasis:entry>  
         <oasis:entry colname="col4">1.96 (0.8)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">SO<inline-formula><mml:math 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">329 (101)</oasis:entry>  
         <oasis:entry colname="col3">1042 (295)</oasis:entry>  
         <oasis:entry colname="col4">76.9 (30)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Mg<inline-formula><mml:math 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">416 (104)</oasis:entry>  
         <oasis:entry colname="col3">854 (162)</oasis:entry>  
         <oasis:entry colname="col4">219 (75)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Ca<inline-formula><mml:math 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">441 (64)</oasis:entry>  
         <oasis:entry colname="col3">894 (234)</oasis:entry>  
         <oasis:entry colname="col4">173 (37)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">K<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">33.6 (5.4)</oasis:entry>  
         <oasis:entry colname="col3">25.9 (4.5)</oasis:entry>  
         <oasis:entry colname="col4">3.55 (1.1)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Na<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">238 (42.1)</oasis:entry>  
         <oasis:entry colname="col3">890 (303)</oasis:entry>  
         <oasis:entry colname="col4">71.7 (23)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Cl<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">137 (57.9)</oasis:entry>  
         <oasis:entry colname="col3">1231 (561)</oasis:entry>  
         <oasis:entry colname="col4">11.8 (3.9)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>24.4 (0.92)</oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>21.6 (0.69)</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>19.2 (0.49)</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p>Mean (SE) water chemistry from ground ice, outflow, and reference water for
the 5 slides, 3 gullies, and 16 slumps where we sampled ground ice exposed
by thermokarst formation. *DOC : DON is a unitless ratio and <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O
is ‰.</p></table-wrap-foot></table-wrap>

      <p>Landscape age modulated the effect of upland thermokarst on water chemistry,
with much larger differences between impacted and undisturbed concentrations
of DOC, NH<inline-formula><mml:math 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>, Cl<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>, and SO<inline-formula><mml:math 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> at sites occurring on
surfaces older than 50 kyr (Fig. 9). Vegetation had a smaller effect on fewer
parameters with only DOC, Ca<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula>, and Cl<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula> differing significantly by
vegetation community independent of development stage, feature type, and
landscape age, with different patterns between vegetation communities for
each solute (Fig. 10).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F9"><caption><p>Mean (<inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>95 % CI) of parameters that varied significantly
by surface age. Impacted and reference concentrations are shown
independently when the interaction between thermokarst impact and surface
age was significant, otherwise results are combined.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f09.pdf"/>

        </fig>

</sec>
</sec>
<sec id="Ch1.S4">
  <title>Discussion</title>
      <p>There is conflicting evidence of the impacts of upland thermokarst on
concentrations and fluxes of DOC, nutrients, and other solutes (Bowden et
al., 2008; Thompson et al., 2012), as well as the intensity and duration of
these effects (Kokelj et al., 2005; Lafreniere and Lamoureux, 2013;
Thienpont et al., 2013). Our spatially extensive sampling of active and
stabilized features revealed that upland thermokarst consistently increases
DOC and other solute concentrations, with a particularly large effect on
inorganic nitrogen. Magnitude and duration of thermokarst effects on water
chemistry differed by feature type and secondarily by landscape age. Most
solutes returned to undisturbed concentrations after feature stabilization,
but elevated inorganic nitrogen and several other parameters persisted in
gully and slump outflows, suggesting that these feature types could have
long-lasting impacts on aquatic nutrient dynamics.</p>
<sec id="Ch1.S4.SS1">
  <title>Patterns of carbon and nitrogen release from upland thermokarst</title>
      <p>We hypothesized that thermokarst would increase or decrease DOC
concentration in surface waters depending on the balance of DOC production
and removal processes active during feature formation. Despite large organic
layer losses and abundant exposed mineral soil (Pizano et al., 2014), upland
thermokarst significantly increased average DOC concentration and yield for
all feature types. Additionally, DOC from active thermokarst features is
3 to 4 times more bio- and photodegradable than active-layer-derived
DOC (Abbott et al., 2014; Cory et al., 2013), changing the implications of
this release at different spatial scales. DOC mobilized by thermokarst is
likely to be mineralized rapidly in receiving soils, streams, and lakes,
accelerating transfer of permafrost carbon to the atmosphere (Vonk et al.,
2013) but reducing the impact of this disturbance on estuaries of the Arctic
Ocean (McClelland et al., 2012; Striegl et al., 2005).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F10"><caption><p>Mean (<inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>95 % CI) of DOC for thermokarst outflow and
reference water from sites occurring on moist acidic (MAT), nonacidic
(MNAT), and shrub tundra. Different letters above panels represent
significant differences between feature types. DOC, Ca<inline-formula><mml:math 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 Cl<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>-</mml:mo></mml:msup></mml:math></inline-formula>
were the only parameters for which vegetation was a significant predictor in
the mixed-effects ANOVA when accounting for development stage, feature type,
and landscape age.</p></caption>
          <?xmltex \igopts{width=170.716535pt}?><graphic xlink:href="https://bg.copernicus.org/articles/12/3725/2015/bg-12-3725-2015-f10.pdf"/>

        </fig>

      <p>Upland thermokarst had a relatively larger effect on aquatic nitrogen than
carbon concentrations, reducing the C : N ratio of dissolved organic matter
and causing substantial and long-lasting release of inorganic nitrogen.
Phosphorus, not nitrogen, is typically the most limiting nutrient in Arctic
freshwater systems (O'Brien et al., 2005; Slavik et al., 2004); however,
nitrogen and silica limit productivity in Arctic estuaries and the Arctic
Ocean (McClelland et al., 2012; Vancoppenolle et al., 2013). If thermokarst
nitrogen release is accompanied by bioavailable phosphorus, more nitrogen
will be retained in inland aquatic ecosystems, whereas if thermokarst
outflows have relatively little phosphorus, a larger proportion of liberated
nitrogen will reach the ocean. Thermokarst can increase phosphorus loading
(Bowden et al., 2008; Hobbie et al., 1999), but the relative impact of
upland thermokarst on nutrient stoichiometry remains an important unknown.</p>
      <p>Along with changes in solute concentrations and characteristics, upland
thermokarst may affect the seasonality of solute flux. For most aquatic
ecosystems in the Arctic, the majority of annual carbon and nutrient load
occurs during snowmelt or early spring (Holmes et al., 2012). While carbon
and nitrogen concentrations in thermokarst outflow do not appear to vary
systematically over the season, thermokarst discharge, which depends
primarily on air temperature and net radiation, peaks in mid- to late summer
(Kokelj and Jorgenson, 2013; Lantuit and Pollard, 2005; Lantz and Kokelj,
2008). Late-season delivery of carbon and nitrogen would have a larger
relative impact on surface water concentrations, further modifying
functioning of Arctic rivers and lakes. This shift could also affect Arctic
estuaries, where nutrients and carbon are taken up quickly during open-water
season but transported to the Arctic Ocean during ice cover (Townsend-Small
et al., 2011).</p>
      <p>Feature morphology strongly influenced magnitude and duration of thermokarst
effects on water chemistry, with slides having a smaller and shorter impact
than gullies or slumps. This could be due to differences in feature depth
and duration of feature growth. In permafrost soil, leachable solutes are
typically highest below the transition layer at the top of the permafrost
table (Keller et al., 2007; Kokelj and Burn, 2003; Malone et al., 2013) and
the age and characteristics of soil carbon differ strongly with depth (Guo
et al., 2007; Neff et al., 2006; Nowinski et al., 2010; Schuur et al.,
2009). Shallow slides are less likely to expose deeper, solute-rich soils to
hydrologic export than slumps and gullies, which cut meters into permafrost.
However, slides caused a similar magnitude of increase as gullies and slumps
for inorganic nitrogen concentration, suggesting that altered dynamics at
the surface rather than depth of disturbance may determine nitrogen
available for export. For all feature types, effects on carbon, nitrogen,
and other solutes were largely limited to the period of active feature
formation, meaning that the influence of upland thermokarst is directly
related to period of active growth. In this regard slides, gullies, and
slumps are dramatically different. Slides typically form suddenly, over a
period of weeks, days, or even hours (Lewkowicz, 2007) and stabilize the
same season they appear (Lafreniere and Lamoureux, 2013). In contrast, large
thaw slumps commonly remain active for 12–50 years (Burn, 2000; Kokelj et
al., 2013; Lewkowicz, 1987), though small slumps stabilize in less than 10
years (Kokelj et al., 2009). Less is known about gully longevity, but based
on average feature size and rates of headwall retreat, they remain active
for 5 to 10 years (Jorgenson and Osterkamp, 2005), with large features
lasting over a decade (Godin and Fortier, 2012). Differences in outflow
chemistry between feature types agree with findings from high-Arctic systems
suggesting that slide formation may have relatively limited impact on water
chemistry (Lewis et al., 2012), and suggest that gullies and slumps, with
their long active periods and influential position in hydrologic networks
(Krieger, 2012), are likely to have a persistent and widespread effect on
aquatic ecosystems.</p><?xmltex \hack{\newpage}?>
</sec>
<sec id="Ch1.S4.SS2">
  <title>Decrease in dissolved methane</title>
      <p>There are several possible mechanisms behind the unexpected 90 % decrease
in dissolved CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> in gully and slump outflows. Greater thaw depth within
features could facilitate infiltration, creating a larger aerated zone where
CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> oxidation can occur (Schuur et al., 2009). Slides may have had no
effect on dissolved CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> because they do not affect thaw depth as
profoundly as gullies and slumps. However soils affected by slides, gullies,
and slumps have partial pressures of CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> higher than or equal to reference
tundra (Abbott and Jones, 2015), suggesting that low CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> in thermokarst
outflows is due to changes in production or consumption in the water column,
rather than in soils. For slumps this decrease may be due to high
concentrations of SO<inline-formula><mml:math 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> released during thermokarst formation.
SO<inline-formula><mml:math 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> is an energetically favorable electron acceptor compared to
the low-molecular-weight organic compounds or CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> used by methanogens
(Dar et al., 2008), and sulfate-reducing bacteria can inhibit methane
production through competition for molecular substrates (Muyzer and Stams,
2008). SO<inline-formula><mml:math 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> concentration was negatively associated with
dissolved CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> across site types and development stages, further
supporting this hypothesis. However, SO<inline-formula><mml:math 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> release does not
explain decreased dissolved CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> in gully outflows since we observed no
change in gully SO<inline-formula><mml:math 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>. One possibility is that high inorganic
nitrogen concentration is stimulating CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> consumption in gully and
slump outflows. While elevated DIN can suppress high-affinity methanotrophs
responsible for CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> oxidation in low-CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> environments, DIN can
stimulate consumption by low-affinity methanotrophs that dominate
consumption in high-CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> environments and are commonly nitrogen-limited
(Bodelier and Laanbroek, 2004). This would explain the large CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>
decrease in gully outflows where CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> concentration was high, and the
lack of response in slide outflows where CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> was 10-fold lower despite
similar changes in DIN concentration.</p>
      <p>Similar concentrations of SO<inline-formula><mml:math 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> have been observed in outflows of
thaw slumps in the Mackenzie Delta (Kokelj et al., 2005; Malone et al.,
2013), and there is evidence of enhanced sulfur availability in lakes
throughout the Arctic (Drevnick et al., 2010). The widespread release of
SO<inline-formula><mml:math 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> from upland thermokarst may have important implications for
carbon cycling as the permafrost region thaws. Increases in freshwater
SO<inline-formula><mml:math 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> could accelerate anaerobic decomposition of organic carbon
liberated from permafrost (Einsele et al., 2001) and suppress CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula>
production after permafrost thaw, modulating one of the key feedbacks from
the permafrost system on global climate (Walter et al., 2006).</p>
</sec>
<sec id="Ch1.S4.SS3">
  <title>Where is thermokarst nitrogen coming from?</title>
      <p>Though primary production in high-latitude terrestrial ecosystems tends to
be limited by nitrogen, suggesting that bioavailable forms of nitrogen
should be retained (Vitousek and Reiners, 1975), there are numerous reports
of inorganic nitrogen loss from landscapes affected by permafrost
degradation (Jones et al., 2005; Mack et al., 2004; McClelland et al.,
2007). Contrary to our hypothesis that high demand for nutrients by
re-establishing plants would decrease nutrient concentrations in thermokarst
outflows during recovery, NH<inline-formula><mml:math 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> concentration was elevated in
stabilized gullies, and in no case was DIN significantly lower in recovering
features than in undisturbed tundra. This suggests that either nitrogen is
not limiting plant growth during revegetation or pathways of nitrogen loss
bypass locations of high uptake (e.g., preferential flow paths below plant
rooting zones).</p>
      <p>Microenvironments in thermokarst can favor deciduous shrub establishment
including nitrogen-fixing species (Lantz et al., 2009), a potential source
for thermokarst nitrogen. However, even in the absence of nitrogen-fixing
species, surface soils in recovering thermokarst features re-accumulate
nitrogen rapidly (Pizano et al., 2014). Upland thermokarst can warm
wintertime soil temperature by up to 6 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C due to conductive heat
flux to soils during summer and added insulation in winter from deeper snow
(Burn, 2000). If nitrogen mineralization continues through the fall and
winter in thawed soils beneath thermokarst scars, hydrologic activity in the
spring or deep shrub roots could transport inorganic nitrogen to the
surface, fueling productivity and hydrologic export. The isotopic signature
of NO<inline-formula><mml:math 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> draining a high-Arctic catchment impacted by upland
thermokarst suggests DIN from thermokarst is derived from the heterotrophic
decomposition of organic matter found in the mineral soil (Louiseize et al.,
2014), supporting this hypothesis. Additionally, or alternatively, a portion
of inorganic nitrogen in upland thermokarst outflow may come from
mineralization of labile dissolved organic matter in the water column or
soil solution. This would explain the strong correlation between DIN
concentration and DOC biodegradability observed in several Arctic and boreal
ecosystems (Abbott et al., 2014; Balcarczyk et al., 2009; Wickland et al.,
2012).</p>
</sec>
<sec id="Ch1.S4.SS4">
  <title>Shifts in landscape-scale water chemistry</title>
      <p>As high latitudes warm, ecosystems are experiencing widespread shifts in
aquatic chemistry including an increase in DOC flux in areas with peat and
thick organic soil (Frey and McClelland, 2009), a decrease in DOC where
organic soil is shallow (McClelland et al., 2007; Petrone et al., 2006;
Striegl et al., 2005), increases in major ion concentrations (Frey and
McClelland, 2009; Giesler et al., 2014; Keller et al., 2010), and increased
inorganic nutrient flux (Jones et al., 2005; McClelland et al., 2007;
Petrone et al., 2006). These changes in catchment-scale solute fluxes have
primarily been attributed to mechanisms associated with gradual thaw such as
deepening of surface flow paths and changes in residence time. However,
thermokarst may also be contributing to these shifts in catchment-scale
chemistry (Frey and McClelland, 2009). The chemical signature of dissolved
organic matter from thermokarst closely matches biodegradable DOC recently
detected in boreal streams and rivers (Abbott et al., 2014; Balcarczyk et
al., 2009; Wickland et al., 2012) and increases in DIN and solutes from
thermokarst match circumpolar changes attributed to a shift towards greater
ground-water inputs (Frey and McClelland, 2009; Frey et al., 2007).</p>
      <p>Currently a scarcity of observations of the spatial extent and distribution
of upland thermokarst features and the annual elemental yields for different
feature and landscape types limits our ability to evaluate the relative
importance of gradual thaw and thermokarst in determining the evolution of
high-latitude biogeochemistry. Though our estimates of DOC and DIN daily
yield are based on individual measurements from a relatively small set of
features, if elemental yields from upland thermokarst are similar to the
range observed here, this spatially limited disturbance may have a large
influence on landscape-level carbon and nitrogen fluxes. A simple scaling
exercise based on projections of permafrost degradation, average feature
lifetimes, and daily yields measured here suggests that though upland
thermokarst is only expected to directly impact 3 % of the total
circum-Arctic watershed by 2100, it may cause a 2.7–23 % increase in
annual circum-Arctic DOC flux and a 2.2–19 % increase in dissolved
inorganic nitrogen averaged over 2050–2100 (see Table S1 for
assumptions). While these fluxes are highly speculative, they underline the
potential of this spatially limited disturbance to influence the rate of
carbon and nitrogen release from thawing permafrost.</p>
</sec>
</sec>
<sec id="Ch1.S5" sec-type="conclusions">
  <title>Conclusions</title>
      <p>Upland thermokarst across the foothills of the Brooks Range caused
substantial increases in inorganic nitrogen, DOC, and other solute
concentrations. Thaw slumps and thermo-erosion gullies had larger impacts on
solute concentrations and are likely more important than slides to surface
water chemistry because they can remain active for multiple years. The
delivery of labile carbon and nutrients such as SO<inline-formula><mml:math 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
inorganic nitrogen to downstream or downslope ecosystems could have
important consequences for offsite carbon cycling, accelerating
decomposition of organic matter in anoxic environments and priming the
decomposition of recalcitrant organic matter. The fact that individual
features can impact entire lakes or river reaches over multiple years in
combination with the large portion of the landscape underlain by ice-rich
permafrost suggests that upland thermokarst may be the dominant disturbance
affecting aquatic ecosystems as the Arctic warms.</p>
</sec>

      
      </body>
    <back><app-group>
        <supplementary-material position="anchor"><p><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="http://dx.doi.org/10.5194/bg-12-3725-2015-supplement" xlink:title="pdf">doi:10.5194/bg-12-3725-2015-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><notes notes-type="authorcontribution">

      <p>B. W. Abbott and J. B. Jones designed the experiment and worked closely on the
manuscript written by B. W. Abbott. B. W. Abbott, S. E. Godsey, and J. R. Larouche carried out
sample collection, preparation, and analysis. All authors helped refine the
experimental design and provided input on the manuscript.</p>
  </notes><ack><title>Acknowledgements</title><p>This work was supported by the National Science Foundation ARCSS program
(OPP-0806465 and OPP-0806394). We thank the many individuals and
organizations that assisted with this study. T. Chapin, T. Schuur, S. Bret-Harte, and B. Risser gave valuable
input on the manuscript. S. Abbott,
A. Olsson, L. Koenig, and P. Tobin, assisted with lab and fieldwork. Toolik
Field Station and CH2M Hill Polar Services provided logistic support. The
National Park Service and Bureau of Land Management facilitated research
permits. Dedicated to A. Bali.
<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?>
Edited by: J. Vonk</p></ack><ref-list>
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