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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-12-2953-2015</article-id><title-group><article-title>A model of the methane cycle, permafrost, and hydrology <?xmltex \hack{\newline}?>of the Siberian
continental margin</article-title>
      </title-group><?xmltex \runningtitle{A model of the methane cycle, permafrost, and hydrology}?><?xmltex \runningauthor{D. Archer}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Archer</surname><given-names>D.</given-names></name>
          <email>d-archer@uchicago.edu</email>
        <ext-link>https://orcid.org/0000-0002-4523-7912</ext-link></contrib>
        <aff id="aff1"><institution>University of Chicago, Department of the Geophysical Sciences, Chicago, USA</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">D. Archer (d-archer@uchicago.edu)</corresp></author-notes><pub-date><day>21</day><month>May</month><year>2015</year></pub-date>
      
      <volume>12</volume>
      <issue>10</issue>
      <fpage>2953</fpage><lpage>2974</lpage>
      <history>
        <date date-type="received"><day>15</day><month>April</month><year>2014</year></date>
           <date date-type="rev-request"><day>3</day><month>June</month><year>2014</year></date>
           <date date-type="rev-recd"><day>26</day><month>March</month><year>2015</year></date>
           <date date-type="accepted"><day>13</day><month>April</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://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015.html">This article is available from https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015.html</self-uri>
<self-uri xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015.pdf">The full text article is available as a PDF file from https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015.pdf</self-uri>


      <abstract>
    <p>A two-dimensional model of a sediment column, with Darcy fluid flow,
biological and thermal methane production, and permafrost and methane
hydrate formation, is subjected to glacial–interglacial cycles in sea
level, alternately exposing the continental shelf to the cold atmosphere
during glacial times and immersing it in the ocean in interglacial times. The
glacial cycles are followed by a “long-tail” 100 kyr warming due
to fossil fuel combustion.</p>
    <p>The salinity of the sediment column in the interior of the shelf can be
decreased by hydrological forcing to depths well below sea level when the
sediment is exposed to the atmosphere. There is no analogous advective
seawater-injecting mechanism upon resubmergence, only slower diffusive
mechanisms. This hydrological ratchet is consistent with the existence of
freshwater beneath the sea floor on continental shelves around the world,
left over from the last glacial period.</p>
    <p>The salt content of the sediment column affects the relative proportions of
the solid and fluid H<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>O-containing phases, but in the permafrost zone
the salinity in the pore fluid brine is a function of temperature only,
controlled by equilibrium with ice. Ice can tolerate a higher salinity in
the pore fluid than methane hydrate can at low pressure and temperature,
excluding methane hydrate from thermodynamic stability in the permafrost
zone. The implication is that any methane hydrate existing today will be
insulated from anthropogenic climate change by hundreds of meters of
sediment, resulting in a response time of thousands of years.</p>
    <p>The strongest impact of the glacial–interglacial cycles on the atmospheric
methane flux is due to bubbles dissolving in the ocean when sea level is
high. When sea level is low and the sediment surface is exposed to the
atmosphere, the atmospheric flux is sensitive to whether permafrost inhibits
bubble migration in the model. If it does, the atmospheric flux is highest
during the glaciating, sea level regression (soil-freezing) part of the
cycle rather than during deglacial transgression (warming and thawing).</p>
    <p>The atmospheric flux response to a warming climate is small, relative to the
rest of the methane sources to the atmosphere in the global budget, because
of the ongoing flooding of the continental shelf. The increased methane flux
due to ocean warming could be completely counteracted by a sea level rise of
tens of meters on millennial timescales due to the loss of ice sheets,
decreasing the efficiency of bubble transit through the water column. The
model results give no indication of a mechanism by which methane emissions
from the Siberian continental shelf could have a significant impact on the
near-term evolution of Earth's climate, but on millennial timescales the
release of carbon from hydrate and permafrost could contribute significantly
to the fossil fuel carbon burden in the atmosphere–ocean–terrestrial
carbon cycle.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
<sec id="Ch1.S1.SS1">
  <title>The Siberian continental shelf system</title>
      <p>The Siberian Arctic continental shelf has been the focus of attention from
scientists and the public at large for its potential to release methane, a
greenhouse gas, in response to climate warming, a potential amplifying
positive feedback to climate change (Shakhova, 2010; Westbrook et al., 2009). The goal of this
paper is to simulate the geophysical and carbon cycle dynamics of the
Siberian continental margin within the context of a basin- and geologic-timescale mechanistic model of the coastal margin carbon cycle called
SpongeBOB (Beneath Ocean Biosphere; Archer et al., 2012). An initial condition for the glacial cycle
simulations was generated by spinning the model up at low resolution over 62
million simulated years. Then the model is driven, at higher resolution, by
cyclic changes in sea level and air temperature resulting from glacial
cycles, to simulate the impact of the hydrological pressure head and
permafrost formation on the fluid flow and methane cycle on the shelf.
Finally, a 100 000-year interglacial interval in the simulation is
subjected to anthropogenic warming of the overlying water and potential
60 m changes in sea level. Sensitivity studies are presented for the
biogenic and thermogenic methane production rates, initial salinity,
geothermal temperature gradient, rates of hydrological flow, and permafrost
impact on gas mobility.</p>
<sec id="Ch1.S1.SS1.SSS1">
  <title>Permafrost</title>
      <p>One component of the simulation is a wedge of frozen sediment (permafrost)
submerged beneath the ocean on the continental shelf of Siberia, left behind
from the Last Glacial Maximum, when the shelves were exposed to the frigid atmosphere by
lowered sea level (Romanovskii and Hubberten, 2001). The ice is thought to provide a seal
to the upward migration of methane gas (Shakhova et al., 2009), especially where ancient
fresh groundwater flow produced a layer of very high saturation ice infill,
a formation called the Ice Complex in Siberia (Romanovskii et al., 2000),
although there are high ice saturations found in the Alaskan Arctic as well
(Zimov et al., 2006).</p>
      <p>With inundation by the natural sea level rise over more than the last 10 000 years, the permafrost is transiently melting, although the time constant for
this is generally long enough for significant frozen volume to remain,
especially in shallower waters which were flooded more recently
(Khvorostyanov et al., 2008a; Nicolsky and Shakhova, 2010; Romanovskii and Hubberten, 2001; Romanovskii et al., 2004;
Shakhova et al., 2009; Taylor et al., 1996). Even overlying water at the freezing temperature can
provoke subsurface melting by providing a warmer boundary condition against
which geothermal heat establishes the subsurface temperature profile, but
with climate warming, the waters could surpass the freezing temperature,
allowing heat to flow from above as well as below (Khvorostyanov et al., 2008b).</p>
      <p>Elevated methane concentrations have been measured in the water column over
the Siberian shelf, even in areas of shallow water where the permafrost
should still be strongly intact (Shakhova, 2010; Shakhova et al., 2005). Chemical and
isotopic signatures of hydrocarbons adsorbed onto surface sediments indicate
a thermal origin (Cramer and Franke, 2005), suggesting that the methane is produced many
kilometers deep in the sediment column. The apparent ability of this
methane to transverse the barrier of the Ice Complex has been attributed to
hypothesized openings in the ice (called “taliks”), resulting from lakes
or rivers on the exposed shelf, or to geologic faults
(Nicolsky and Shakhova, 2010; Romanovskii et al., 2004; Shakhova et al., 2009).</p>
</sec>
<sec id="Ch1.S1.SS1.SSS2">
  <title>Salt</title>
      <p>Dissolved salt in the pore waters can impact the timing of thawing
permafrost (Nicolsky and Shakhova, 2010; Shakhova et al., 2009). When sea level drops and exposes the
top of the sediment column to the atmosphere and freshwater, the salinity
of the subsurface pore waters can be flushed out by hydrological groundwater
flow, driven by the pressure head from the elevated terrestrial water table
above sea level. The boundary between fresh and salty pore water tends to
intersect the sediment surface at the water's edge (Moore et al., 2011). From
there, the boundary tends to dip landward, to a depth of approximately 40 m below sea level for every 1 m of elevation of the table water.
The ratio of water table elevation to freshwater lens depth is driven by the
relative densities of fresh- and salt water, as the fluid seeks an isostatic
balance in which the freshwater displaces an equal mass of salt water
(Verrjuit, 1968).</p>
      <p>The SpongeBOB model has been modified to simulate the processes responsible
for these observations. We do not attempt to simulate a detailed outcropping
history over a 62-million-year spinup time of the sediment column but rather
demonstrate the general process by subjecting the nearly complete sediment
column to a one-time sea level lowering, exposing the continental shelf to
groundwater forcing (see Sect. A4). After a few million years,
the sediment column subsides, due to compaction and the absence of sediment
deposition, resulting in a sediment column that has been considerably
freshened by the atmospheric exposure. This freshening persists in the model
for millions of years because there is no corresponding “salt-water pump”
during high sea level stands. This behavior is consistent with the discovery
of vast nearly fresh aquifers in currently submerged continental shelf
regions around the world (Post et al., 2013), left over from groundwater
forcing during the Last Glacial Maximum.</p>
</sec>
<sec id="Ch1.S1.SS1.SSS3">
  <title>Carbon</title>
      <p>Another component of the simulation is the Yedoma, deposits of wind-blown
dust and organic carbon that accumulated on the coastal plains of exposed
continental shelves during glacial times (Zimov et al., 2006). The
deposits contain a substantial fraction of organic carbon, consisting of
grass roots and remains preserved by the freezing conditions. When they
thaw, they begin to release 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 methane to the atmosphere
(Dutta et al., 2006; Schuur et al., 2008; Zimov et al., 2006). Oxidation of the
carbon can give off enough heat to accelerate the melting driven by primary
climate forcing (Khvorostyanov et al., 2008b).</p>
</sec>
</sec>
<sec id="Ch1.S1.SS2">
  <title>Models of methane hydrate in the permafrost zone</title>
      <p>The dynamics of the permafrost layer, and its present state, have been
extensively modeled within the context of detailed maps of the crust and sediment structure
(Gavrilov et al., 2003; Nicolsky and Shakhova, 2010; Nicolsky et al., 2012; Romanovskii and Hubberten, 2001;
Romanovskii et al., 2005). Methane hydrate modeling has been done in the Arctic and applied to the
Siberian continental slope (Reagan, 2008; Reagan and Moridis, 2009; Reagan et al., 2011), but only one
calculation has been done in the context of permafrost formation
(Romanovskii et al., 2005) as found on the shelf. Romanovski (2005)
modeled the extent of the methane hydrate stability zone through glacial
cycles but based the calculations on marine salinity values when
calculating the stability of hydrate. I will argue that in sub-freezing
conditions (in the permafrost zone) the only water available for hydrate
formation will be in a saline brine that would be in equilibrium with ice at
the local temperature. This formulation restricts hydrate stability from the
permafrost zone to a greater depth below the sea floor than if the salinity
was unaffected by the formation of ice.</p>
</sec>
<sec id="Ch1.S1.SS3">
  <title>Outline of this work</title>
      <p>The model description in Sect. 2 begins with a description of the
previously published aspects of the SpongeBOB model as it is applied to the
Siberian margin (Sect. 2.1). New developments in the code include pressure-head-driven groundwater flow (Sect. 2.2), permafrost formation and its impacts on the
thermodynamics of ice and hydrate (Sect. 2.3), and the calculation of the methane
flux to the atmosphere (Sect. 2.4). The procedure for generating the initial-condition sediment column for the glacial–interglacial cycles (Sect. 2.5) is
presented along with a description of the forcings imposed to generate the
glacial–interglacial cycles (Sect. 2.6) and the subsequent Anthropocene (Sect. 2.7).
The formulation and rationale for the sensitivity studies is given in Sect. 2.8.</p>
      <p>The Results section (Sect. 3) includes a discussion of the model behavior through
the glacial–interglacial cycles (Sect. 3.1) and in response to anthropogenic
global warming scenarios (Sect. 3.2). A summary of model sensitivity study results
is given in Sect. 3.3 and comparison with field observations in Sect. 3.4.</p>
      <p>The Discussion section (Sect. 4) includes the model limitations and critical
issues for future development (Sect. 4.1), followed by the robust features of the
model simulations (Sect. 4.2).
<?xmltex \hack{\newpage}?></p>
</sec>
</sec>
<sec id="Ch1.S2">
  <title>Model description</title>
<sec id="Ch1.S2.SS1">
  <title>SpongeBOB application to the Siberian continental margin</title>
      <p>SpongeBOB is a two-dimensional basin spatial-scale and geological-timescale
model for the methane cycle in continental-margin sediments. The model,
configured for a passive margin basin, was described by Archer et al. (2012) and applied to the Atlantic coast of the United States. The
bottom boundary is bedrock, and accumulation timescales are millions of
years, as sediment is introduced as coastal riverine material and settles
on the sea floor. Isostatic adjustment and crustal subsidence make room for
the accumulation of 5–10 km of sediment, which progrades seaward in
sigmoidal packages, driven by a maximum sediment accumulation rate just off
the shelf break.</p>
      <p>Here the model framework is used as a representation of the continental
shelf of Siberia, although the tectonic and depositional histories of the
region are heavily impacted by vertical tectonic motions not represented in
the model. The crust underlying the continental shelf area has been
alternately rising and subsiding in blocks called horsts and grabens
(Nicolsky et al., 2012). The sediment cover on the grabens is thick, much
thicker than it is in the horsts, and thick enough for thermal methane
production. The thickness of the sediment cover in the model ranges from 5 to 10 km throughout the domain, reminiscent of the grabens
(subsiding blocks) because thermogenic methane is an essential part of the
simulations.</p>
      <p>The model maintains a concentration of particulate organic carbon with
which it predicts rates of methanogenesis. However, because the depositional
histories and organic-carbon concentrations in the Siberian continental
margin are not well constrained, the rates of biological and thermal methane
production predicted by the model are unreliable predictors of reality. For
this reason, methanogenesis rates in the model are scaled arbitrarily as
tunable model inputs. The depth distributions of the sources depend mostly
on temperature, an easier variable to predict than organic-carbon
degradation activity.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>New model development: groundwater hydrology</title>
<sec id="Ch1.S2.SS2.SSS1">
  <title>Pressure head</title>
      <p>When the sediment column is exposed to the atmosphere, the pressure field
from the variable elevation of the water table (the pressure head) begins to
affect the fluid flow. The pressure head for a fluid particle at the depth
of the water table varies in the following way:

                  <disp-formula id="Ch1.Ex1"><mml:math display="block"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mtext>head</mml:mtext></mml:msub><mml:mo>(</mml:mo><mml:mi>z</mml:mi><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mi>g</mml:mi><mml:munderover><mml:mo movablelimits="false">∫</mml:mo><mml:mi>z</mml:mi><mml:mrow><mml:msub><mml:mi>z</mml:mi><mml:mtext>wt</mml:mtext></mml:msub></mml:mrow></mml:munderover><mml:msub><mml:mi mathvariant="italic">ρ</mml:mi><mml:mtext>seawater</mml:mtext></mml:msub><mml:mi mathvariant="normal">d</mml:mi><mml:mi>z</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

            where <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>z</mml:mi><mml:mi mathvariant="normal">wt</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is the elevation of the water table, which affects the
pressure throughout the fluid column, and the integral of the fluid density
allows the pressure at depth to be affected by the salinity and temperature
of the water above. The depth of the water table is a prognostic variable in
the model. In these simulations, however, the water table remains very close
to the sediment surface, as unsaturated soil produced by subsurface flow is
quickly replenished by hydrological recharge.</p>
</sec>
<sec id="Ch1.S2.SS2.SSS2">
  <title>Pore fluid flow</title>
      <p>The pressure head acts in concert with the excess pressure P<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:math></inline-formula>, as
defined by Archer et al. (2012), to drive horizontal Darcy flow
through the sediment. The value of <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is determined from the
porosity and sediment load of the sediment in each grid box. An assumed
sediment rheology is used to calculate the load-bearing capacity of the
solid matrix within a given grid cell. <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is calculated by
assuming that the load of the solid phase overlying the grid cell that is
not carried by the solid matrix must be carried by the <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> in the
fluid phase.</p>
      <p>The horizontal flow is

                  <disp-formula specific-use="align"><mml:math display="block"><mml:mtable displaystyle="true"><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:msub><mml:mi>u</mml:mi><mml:mrow><mml:mtext>Darcy</mml:mtext><mml:mo>,</mml:mo><mml:mi>i</mml:mi><mml:mo>→</mml:mo><mml:mi>i</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mfrac><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>h</mml:mi><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>h</mml:mi><mml:mo>,</mml:mo><mml:mi>i</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub></mml:mrow><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mi mathvariant="italic">μ</mml:mi></mml:mrow></mml:mfrac><mml:mfrac><mml:mrow><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mrow><mml:mtext>excess</mml:mtext><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mrow><mml:mtext>excess</mml:mtext><mml:mo>,</mml:mo><mml:mi>i</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mrow><mml:mtext>head</mml:mtext><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mrow><mml:mtext>head</mml:mtext><mml:mo>,</mml:mo><mml:mi>i</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>x</mml:mi><mml:mi>i</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>x</mml:mi><mml:mrow><mml:mi>i</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:mfrac><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula>

              while the vertical flow in the model is driven only by compaction pressure

                  <disp-formula id="Ch1.Ex4"><mml:math display="block"><mml:mrow><mml:msub><mml:mi>w</mml:mi><mml:mrow><mml:mtext>Darcy</mml:mtext><mml:mo>,</mml:mo><mml:mi>j</mml:mi><mml:mo>→</mml:mo><mml:mi>j</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mfrac><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>v</mml:mi><mml:mo>,</mml:mo><mml:mi>j</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mi mathvariant="italic">μ</mml:mi></mml:mfrac><mml:mfrac><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mrow><mml:mtext>excess</mml:mtext><mml:mo>,</mml:mo><mml:mi>j</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mrow><mml:mtext>excess</mml:mtext><mml:mo>,</mml:mo><mml:mi>j</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub></mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>z</mml:mi><mml:mi>j</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>z</mml:mi><mml:mrow><mml:mi>j</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msub><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:mfrac><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

            where <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>h</mml:mi><mml:mo>,</mml:mo><mml:mi>i</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> is the horizontal permeability at horizontal cell index <inline-formula><mml:math display="inline"><mml:mi>j</mml:mi></mml:math></inline-formula>,
<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>v</mml:mi><mml:mo>,</mml:mo><mml:mi>j</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> is vertical permeability at vertical index <inline-formula><mml:math display="inline"><mml:mi>j</mml:mi></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">μ</mml:mi></mml:math></inline-formula> is the
viscosity, and <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>x</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:mi>z</mml:mi></mml:mrow></mml:math></inline-formula> are cell dimensions. Notes on
numerical issues are given in the Supplement.</p>
</sec>
<sec id="Ch1.S2.SS2.SSS3">
  <title>Canyons</title>
      <p>The model as described so far represents a laterally homogeneous slab, a
poor approximation of hydrology above sea level because of the formation of
canyons and river networks in a real drained plateau. The depth of the water
table in a river canyon is depressed, relative to the surroundings, to the
depth of the canyon. The water table is higher in between the canyons
because of recharge, and the difference in head drives lateral flow, the
canyons acting to drain the sediment column.</p>
      <p>The model formulation has been altered to represent these mechanics in a
simplified way. Rather than expand the model into the full third dimension,
the two-dimensional field of the model is held to represent the sediment column at a
hypothetical ridge crest, as altered by an adjacent canyon. The canyon
elevation is represented by <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>z</mml:mi><mml:mi mathvariant="normal">canyon</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and its width by a scale <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>y</mml:mi><mml:mi mathvariant="normal">canyon</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. A cross-column flow velocity <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mtext>Darcy,  j</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is calculated as

                  <disp-formula id="Ch1.Ex5"><mml:math display="block"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mrow><mml:mtext>Darcy</mml:mtext><mml:mo>,</mml:mo><mml:mi>j</mml:mi></mml:mrow></mml:msub><mml:mo>=</mml:mo><mml:mfrac><mml:mrow><mml:msub><mml:mi>k</mml:mi><mml:mrow><mml:mi>h</mml:mi><mml:mo>,</mml:mo><mml:mi>j</mml:mi></mml:mrow></mml:msub></mml:mrow><mml:mi mathvariant="italic">μ</mml:mi></mml:mfrac><mml:mfrac><mml:mrow><mml:mo>(</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mtext>head, canyon</mml:mtext></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mtext>head</mml:mtext></mml:msub><mml:mo>)</mml:mo></mml:mrow><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>y</mml:mi><mml:mtext>canyon</mml:mtext></mml:msub></mml:mrow></mml:mfrac><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>

            where <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mtext>head, canyon</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is the pressure head as a function of depth in the
hypothetical canyon, calculated assuming that the water table outcrops at
<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>z</mml:mi><mml:mi mathvariant="normal">canyon</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and that the temperatures in the sediment column have adjusted
to the formation of the canyon such that the near-surface geothermal
gradient is the same between the hypothetical canyon and the bulk sediment
column. The lateral “drainage” flow (<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mrow><mml:mi mathvariant="normal">Darcy</mml:mi><mml:mo>,</mml:mo><mml:mi mathvariant="normal">j</mml:mi></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> drives vertical
velocities by continuity.</p>
      <p>The horizontal distance scale <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>y</mml:mi><mml:mi mathvariant="normal">canyon</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is somewhat arbitrary
and difficult to constrain, given that, in the reality of river networks, the
distance to the nearest canyon from any point in the domain is likely to be
a function of altitude, distance from the coast, and time. Another poorly
resolved factor is the depth of the canyon. In reality, canyons cut into a
plateau following a dynamic that erosion is proportional to slope, stopping
at sea level. As a simplification the model is set to hold the canyon depth
at current sea level throughout the simulation.</p>
      <p>In the real fractal geometry of canyons, the spacing between canyons across
a plain is similar to the width of the plain (length of the canyons), so the
base simulation assumes a canyon width of 100 km, based on the width scale of the continental shelf of more than 100 km.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Permafrost</title>
<sec id="Ch1.S2.SS3.SSS1">
  <title>Thermodynamics of ice and hydrate</title>
      <p>The ice model is based on an assumption of thermodynamic equilibrium, in
which the heat content of the cell is distributed between the pure ice,
hydrate, and brine phases, while the salt content is restricted to the
brine. Notes on numerical implementation are given in the Supplement Text S2.</p>
      <p>In the permafrost zone where ice is present, the salinity of the brine
creates an ice freezing point depression that matches the local temperature.
This equilibrium salinity is higher than methane hydrate can tolerate,
excluding hydrate from thermodynamic stability. For a more detailed
examination of the role of the brine salinity in determining the relative
stabilities of ice and hydrate, see the Supplement Text S3.</p>
</sec>
<sec id="Ch1.S2.SS3.SSS2">
  <title>Other impacts</title>
      <p>Permafrost formation has several impacts on the methane cycle in the model.
Biogenic methanogenesis is assumed to be stopped in the ice fraction of a grid
cell (which approaches unity but never reaches it in the model, due to the exclusion of salt into brine). Bubble transport in the model balances bubble
production, driven by a small and not very well constrained standing bubble
concentration within the pore space. It is generally assumed
(Shakhova et al., 2010b) that permafrost inhibits gas transport through the sediment
column, both based on sediment column carbon and hydrogen budgets
(Hunt, 1995) and on the tight seal provided by the Ice Complex. The seal
provided to Arctic lakes, which can drain overnight if the seal is breached,
also lends credence to this idea. In the model, this effect was simulated by
stopping gas transport completely when a grid cell exceeds 50 % ice
fraction (with sensitivity runs assuming 10, 30, 70, and
90 %).</p>
</sec>
</sec>
<sec id="Ch1.S2.SS4">
  <title>Atmospheric methane fluxes</title>
      <p>Bubbles emerging from the sediment column into the water column of the ocean
may dissolve in the water column, or they may reach the sea surface, a
direct methane flux to the atmosphere (Westbrook et al., 2009). In the model,
bubble dissolution in the water column is assumed to attenuate the bubble
flux according to the water depth, with an <inline-formula><mml:math display="inline"><mml:mi>e</mml:mi></mml:math></inline-formula>-folding attenuation scale of 30 m (Gentz et al., 2014; Portnov et al., 2013; Westbrook et al., 2009). In reality, a
low-flux gas seep, producing small bubbles, will probably not reach as far
into the water column as a 30 m scale height, while a faster seep can
reach further. Methane dissolved in the water column, in reality, may
survive oxidation (time constant of about a year) and degas to the
atmosphere, but this possibility is not included in the model. For land grid
points (exposed to the atmosphere by lowered sea level), any upward bubble
flux at the sediment surface is assumed to be released 100 % to the atmosphere.
The model neglects methane oxidation in soils, as well as many other
terrestrial processes, such as thaw bulbs beneath bodies of water
(Walter et al., 2006) and the seasonal cycle of melting and thawing in the
surface active layer (see the discussion in Sect. 4.1).</p>
</sec>
<sec id="Ch1.S2.SS5">
  <title>Initial condition</title>
<sec id="Ch1.S2.SS5.SSS1">
  <title>Rationale for spinup</title>
      <p>The point of the spinup phase is to generate an initial condition for the
glacial cycle simulations. The more usual approach in modeling hydrates is
to start with an ad hoc initial condition (Reagan, 2008; Reagan and Moridis, 2009; Reagan et al., 2011).
For SpongeBOB the model state at any time is the result of the time history
of sedimentation, which is driven by the time-evolving depth of the sea
floor and interacts with isostatic adjustment of the crust. The simplest
way to generate an initial condition in the model without a startup
transient is to spin the model up from bedrock. The duration of the spinup
phase is 62 million years, roughly consistent with the timescale since the
opening of the Laptev Rift. The first 60 Myr used a relatively coarse
resolution, as shown in Fig. 1a. For the glacial–interglacial
experiments, the initial condition was interpolated to a higher-resolution
grid in the vertical, as shown in Fig. 1b.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1"><caption><p>Domain of the model as applied to the Laptev Sea continental shelf
and slope. This is the result of 62 million years of sediment accumulation
on the crust, isostatic subsidence, pore fluid flow, and thermal diffusion,
used as the initial condition for glacial–interglacial cycle and climate
change simulations. Color indicates temperature. <bold>(a)</bold> Full view. Black line
shows the bottom of the crust, which grades smoothly from continental on the
left into ocean crust through most of the domain on the right. <bold>(b)</bold> Close-up showing increased model resolution in the upper kilometer of the sediment
column.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f01.pdf"/>

          </fig>

</sec>
<sec id="Ch1.S2.SS5.SSS2">
  <title>Sediment column salt content</title>
      <p>When sea level drops such that the surface of the sediment column outcrops
to the atmosphere, the pore fluid becomes subject to the pressure head
driving it seaward and to freshwater recharge from precipitation. The
pressure head forcing and the buoyancy of the sediment fluid column combine
to create a mechanism to excavate salinity from the upper sediment column
to depths well below sea level. The salinity of the sediment column tends to
be ratcheted down by exposure to the atmosphere because there is no
comparable advective pump for the reinvasion of seawater when sea level rises.</p>
      <p>A “prefreshened” sediment column was constructed by dropping sea level by
120 m and holding it there for millions of years. The sediment column
subsides back into the ocean over a few million years, but the fresh imprint
of the hydrological flow persists for millions of years (Fig. 2a and
Text S4). If the sediment surface never outcrops, the pore
salinities remain nearly uniform and marine (Fig. 2b). Particulate organic
carbon (POC) concentrations are highest just off the shelf break (Fig. 3) because this is where most of the sediment is deposited, and because the
sedimentary material is richest in POC in shallow ocean water depths
(Archer et al., 2012). Methane concentration (Fig. 4a) closely mirrors the
solubility of dissolved methane, resulting in near-saturation concentrations
through most of the model domain (Fig. 4b). The prefreshened (Fr) versus
marine (Mr) initial conditions are taken as end member salinity sensitivity
runs (see Table 1).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><caption><p>Pore water salinity. <bold>(a)</bold> The fully marine case, in which the
sediment column has always been submerged underneath a time-invariant sea
level. <bold>(b)</bold> Result of sediment column freshening by hydrological groundwater
flow, driven by the pressure head resulting from a water table higher than
sea level. A movie of the transition from marine to freshened (the origin of
<bold>b</bold>) can be seen at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig2.movie.gif.</uri></p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f02.pdf"/>

          </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p>Nomenclature of the model scenarios and sensitivity runs.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="2">
     <oasis:colspec colnum="1" colname="col1" align="justify" colwidth="60pt"/>
     <oasis:colspec colnum="2" colname="col2" align="justify" colwidth="300pt"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Fr</oasis:entry>  
         <oasis:entry colname="col2">The sediment column has been prefreshened by previous exposure to hydrological forcing.</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Mr</oasis:entry>  
         <oasis:entry colname="col2">Initial salinities are close to marine.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">SL</oasis:entry>  
         <oasis:entry colname="col2">Sea level changes with constant air and water temperatures.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">GL</oasis:entry>  
         <oasis:entry colname="col2">SL <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> glacial cycles in air and water temperature.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">GW</oasis:entry>  
         <oasis:entry colname="col2">A long-term global warming scenario, a peak and long-tail temperature perturbation consistent 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> release and cessation of the glacial sawtooth forcing.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">GW <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> SL</oasis:entry>  
         <oasis:entry colname="col2">Adds geologic-timescale sea level rise due to anthropogenic climate change, based on correlation between temperature and sea level in the geologic past (10 m <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C<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>).</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Ctl</oasis:entry>  
         <oasis:entry colname="col2">An extended interglacial with no CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> release forcing.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"><inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> LD</oasis:entry>  
         <oasis:entry colname="col2">Land deposition of carbon-rich Yedoma. Base case is 10 m 100 kyr<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>, with sensitivity runs using 30 and 100 m 100 kyr<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> accumulation of 30 % POC material. Movies in the Supplement are identified by the tags Land30 and Land100.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"><inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> TG</oasis:entry>  
         <oasis:entry colname="col2">Thermogenic methane production rate sensitivity runs, scaling the rate from the spinup result by factors of 10 and 100. Movies in the supplemental material are identified by the tags TGenX10 and TGenX100.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"><inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> Geotherm</oasis:entry>  
         <oasis:entry colname="col2">Sensitivity of ice and hydrate cycles on the geothermal temperature gradient. Temperatures from the base simulation were adjusted when calculating the stability of ice and hydrate to simulate the impact of geothermal heat fluxes on hydrate stability. Note that other aspects of the sediment column, including the solubility of methane, retained the original temperatures. Heat fluxes simulated include 25 mW 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>, 37.5, 50 (base), 62.5, and 75. Movies of the non-base runs are identified by tags HF050, HF075, HF125, and HF150.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Ice and Bubble Transport</oasis:entry>  
         <oasis:entry colname="col2">When the ice fraction exceeds a threshold value methane gas flow is disabled. Base case is 50 %; variants are 10, 30, 70, and 90 %, identified by the tags Ice10, Ice30, Ice70, and Ice90.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">No Ice</oasis:entry>  
         <oasis:entry colname="col2">The ice phase is disallowed in the thermodynamic calculation. Movies in the supplemental material include salinity. The files are tagged as NoIce</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">No Salt from Ice</oasis:entry>  
         <oasis:entry colname="col2">Ice is allowed to form, but it does not affect the salinity as it determines methane hydrate stability. Movie files are tagged as NoSalFromIce.</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1">Permeable Channels</oasis:entry>  
         <oasis:entry colname="col2">Increasing vertical permeability by a factor of 10 every fifth grid cell to generate heterogeneity in the flow. Tagged as PermChan.</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">No Horizontal Flow</oasis:entry>  
         <oasis:entry colname="col2">Horizontal flow is disabled. Tagged as NoHFlow.</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><caption><p>Particulate organic carbon (POC) concentration. Highest values are
found in the sediment depocenter just off the continental shelf break. “Wt.” stands for
“weight”.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f03.pdf"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p>Initial distribution of dissolved methane. <bold>(a)</bold> Concentration in
moles m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. Panels <bold>(b–d)</bold> show <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Ω</mml:mi><mml:mo>=</mml:mo></mml:mrow></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>/CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">4</mml:mn><mml:mo>(</mml:mo><mml:mi mathvariant="normal">sat</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:math></inline-formula> deviation from
equilibrium: <bold>(b)</bold> of the marine (salty) initial condition, <bold>(c)</bold> of the
prefreshened initial condition (note depletion in near-surface near-shore
sediments in the upper left), and <bold>(d)</bold> including permeable channels every five
grid points plus prefreshening.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f04.pdf"/>

          </fig>

</sec>
</sec>
<sec id="Ch1.S2.SS6">
  <title>Glacial cycle forcing</title>
      <p>Beginning from an entirely submerged initial condition, the model is
subjected to 100 kyr sawtooth cycles of sea level ranging between <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>120 to
<inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>20 m from the initial sea level (starting at <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>120 for prefreshened and 0 for pure marine; Fig. 5a). The model forcing scenarios are
summarized, with their abbrevations, in Table 1.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5"><caption><p>Time-dependent forcing for the glacial–interglacial
simulations and the global warming scenarios. <bold>(a)</bold> Sea level is imposed as a
sawtooth 100 kyr cycle, with interglacial intervals shaded. The GW <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> S
simulation tracks potential changes in sea level on long timescales due to
fossil fuel CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> release, following a covariation from the geologic past
of 15 m <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C<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>. The GW and control simulations hold sea level
at interglacial levels. <bold>(b)</bold> Ocean temperature
forcings.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f05.pdf"/>

        </fig>

<sec id="Ch1.S2.SS6.SSS1">
  <title>Sea level</title>
      <p>The simplest scenario (SL) varies the sea level while keeping the air and
water temperatures time-invariant. The sea level air temperature is
maintained at 0 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. This simulation is nearly permafrost-free,
with a small exception where the altitude of the sediment surface is much
higher than sea level (due to the lapse rate in the atmosphere). There is no
deposition of sediment above sea level in this simulation.</p>
</sec>
<sec id="Ch1.S2.SS6.SSS2">
  <title>Glacial climate</title>
      <p>Permafrost formation is added in simulation GL, in which the air temperature
is reduced to <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>16 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C at sea level, linearly with the glacial sea
level fall (Fig. 5b). In the ocean, shelf waters are always <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.8 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, but an interglacial subsurface temperature maximum of
1 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C at 200 m decreases to <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>1.8 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C during glacial
times.</p>
</sec>
<sec id="Ch1.S2.SS6.SSS3">
  <title>Deposition of carbon on land</title>
      <p>The deposition of organic-rich sediments when the surface is exposed to the
atmosphere (Yedoma: represented as accumulation of 10 m in 100 kyr,
with 30 % POC) is added in scenarios SL <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> LD and GL <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> LD (LD for land
deposition).</p>
</sec>
</sec>
<sec id="Ch1.S2.SS7">
  <title>Anthropogenic global warming forcing</title>
<sec id="Ch1.S2.SS7.SSS1">
  <?xmltex \opttitle{Long-term climate impact from CO${}_{{2}}$ addition}?><title>Long-term climate impact from CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> addition</title>
      <p>The global warming (GW) scenario begins from a high sea level interglacial
state and raises the temperature following the climate impact of the
“spike and long-tail” time distribution of a slug of new CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> added to
the atmosphere (Archer et al., 2009; Fig. 8). There is a stage of fast
atmospheric drawdown as CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> invades the ocean, but once the ocean,
atmosphere, and land surface reach equilibrium (after a few hundred years),
the CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> content of the entire biosphere begins to relax toward an
initial “natural” value, on timescales of hundreds of thousands of years,
by weathering reactions with carbonate and siliceous solid rocks. The net
result is a CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> drawdown that can be expressed as the sum of several
exponential functions in time, with timescales ranging from 10<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> to 10<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">6</mml:mn></mml:msup></mml:math></inline-formula> years.</p>
      <p>Changes in water column temperature are assumed to be equal to those of the
atmosphere, following paleoceanographic reconstructions (Martin et al., 2002)
and long-term coupled ocean–atmosphere circulation model experiments
(Stouffer and Manabe, 2003). The GW scenario imposes this temperature change on the water
column, relaxing toward equilibrium with the atmospheric CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> trajectory
with a time constant of 100 years.</p>
</sec>
<sec id="Ch1.S2.SS7.SSS2">
  <title>Long-term behavior of sea level</title>
      <p>The effect of sea level rise is added to create a second global warming
scenario, GW <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> SL. On timescales of thousands of years, the sea level
response to changing global temperature is much stronger than the sea level
response over the coming century, as prominently forecast by the IPCC.
The reconstruction of sea level and global temperature covariation in the
geologic past (glacial times to Eocene hothouse) reveals a covariation of
10–20 m <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C<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> (Archer and Brovkin, 2008). The global warming with sea
level scenario assumes an equilibrium sea level response of 15 m <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C<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> which it relaxes toward with a time constant of 1000 years.</p>
</sec>
</sec>
<sec id="Ch1.S2.SS8">
  <title>Sensitivity studies</title>
      <p>A strategy for dealing with the many uncertainties in the model formulation
and parameterization is to do sensitivity studies to determine which of the
unknowns are most significant. The model sensitivity studies are summarized
in Table 1. Sensitivity studies on the rates of methane production have
already been mentioned, as have the prefreshened versus marine initial
conditions, representing uncertainty in the salt content of the sediment
column. Other model sensitivity runs include the geothermal temperature
gradient and a parameterization of the permafrost inhibition of bubble
migration. Several altered-physics runs were done – one adding vertical
permeable channels, one disabling horizontal flow, and several to evaluate
the impact of ice formation on methane hydrate stability.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results</title>
<sec id="Ch1.S3.SS1">
  <title>Glacial cycles</title>
<sec id="Ch1.S3.SS1.SSS1">
  <title>Salinity</title>
      <p>In the “prefreshened” initial condition (Fr), millions of years have
elapsed since the previous exposure of the sediment to hydrological forcing,
but a core of freshwater remains. Salinities near the sediment surface have
grown saltier due to diffusive contact with seawater (Fig. 6, left). A
fully marine initial condition (Mr; Fig. 6, right) was initialized from
the unfreshened case, in which sea level was held at a fixed value
throughout the 65 Myr spinup of the sediment column. The salinities are
nearly uniform in this case.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6"><caption><p>Colors indicate salinity in the unfrozen pore fluid of the
sediment column. Thin solid black contours show the frozen fraction of the
pore space. Heavy black stippled contour shows the stability boundary of
methane hydrate as a function of temperature, pressure, and unfrozen pore
fluid salinity. Left side: previously prefreshened initial condition. Right
side: pure marine initial condition. Panels <bold>(c–d)</bold> show lowered sea level (from 70 kyr in
Fig. 8) but warm air temperatures prevent permafrost formation.
Panels <bold>(e–f)</bold> show glacial conditions of lowered sea level (70 kyr) and atmospheric temperature
of <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>17 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C driving permafrost formation. The prefreshened and
the marine initial conditions differ in the frozen fraction of sediment, but
the salinity of the unfrozen fluid, a correlate of the activity of water,
depends only on the temperature. Panels <bold>(g–h)</bold> show rising sea level (at 90 kyr in Fig. 8)
during an interglacial interval. Movies of the glacial cycles (GL) with the
prefreshened initial condition can be seen at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig6a.movie.gif</uri>, and movies of the marine initial
condition can be seen at
<uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig6b.movie.gif</uri>.</p></caption>
            <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f06.pdf"/>

          </fig>

      <p>When the sediment surface is re-exposed to the atmosphere during an interval
of low sea level, in the absence of ice formation (simulation SL), the
surface layer tends to freshen relatively quickly due to the hydrological
forcing, although a subsurface salinity maximum persists (Fig. 6c and d).
If the air temperatures are cold enough to form ice (simulation GL), surface
salinities in the model increase to up to nearly 190 psu in both the prefreshened and pure marine cases (Fig. 6e and f). By the next
interglacial period (Fig. 6g and h), ice near the sediment surface has
melted enough for near-surface pore waters to reach relatively low
salinities.</p>
</sec>
<sec id="Ch1.S3.SS1.SSS2">
  <title>Pressure and flow</title>
      <p>The effect of the glacial–interglacial sea level and climate forcing on
the pressures and flow velocities is shown in Fig. 7. On a spatial scale
of the entire model domain (Fig. 7, left), the highest driving pressures
are found at the base of the sediment column, underneath the region of
maximum sediment accumulation (the depocenter just off the shelf break).
Changes in sea level drive large fluctuations in the pressure head
(contours) extending to bedrock. In the near-surface continental shelf
(Fig. 7, right), the driving pressure variations are dominated by the
pressure head, driven by sea level changes. The formation of permafrost (GL,
Fig. 7e and f) seals the upper sediment column to fluid flow.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7"><caption><p>Pore fluid pressure forcing and flow through the glacial cycles.
Left: colors indicate <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">head</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, solid contours are ice
fraction, and dashed contours are <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">head</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>. Right: colors indicate
<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">head</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>; note different color scale from left. Initial
refers to the prefreshened initial condition. “Low Sea Level” refers to
simulation SL. “Glacial” and “Interglacial” refer to simulation GL.
Dashed contours indicate ice fraction; vectors indicate fluid velocity. Movies can be
seen at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig7a.movie.gif</uri> and
<uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig7b.movie.gif</uri>.</p></caption>
            <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f07.pdf"/>

          </fig>

      <p>When sea level rises again, in the model configuration including permafrost,
there is a strong pulse of downward flow following partial melting of the
permafrost (Fig. 7h). It is possible that this flow, which lasts a few
thousand years, is an artifact of the elastic model configuration, in which
the release of a load (by submergence of the upper sediment column into the
ocean) provokes the expansion of pore spaces in the sediment. The anomalous
flow, integrated over its duration, could displace the pore fluid by about
40 m, which is less than one grid cell. The model configuration without
the sealing effect of permafrost (SL) does not show this pulse of invasive
flow on sea level rise.</p>
</sec>
<sec id="Ch1.S3.SS1.SSS3">
  <title>Methane cycle</title>
      <p>There are multiple ways in which the glacial cycles of sea level and air and
water temperature might impact the flux of methane to the atmosphere.
Submergence in the ocean is one modulating factor because the emerging
bubbles dissolve in the ocean rather than reaching the atmosphere. Another
factor is the deposition of high-POC surface soils during low sea level
stands and its exposure to degradation later when the permafrost soils
melt. A third factor is permafrost, impeding gas and fluid flow and
excluding dissolved methane and salt from ice formation. The impacts of
these processes are assessed by comparing the results from model
configurations with and without each process in question.</p>
</sec>
</sec>
<sec id="Ch1.S3.SSx1" specific-use="unnumbered">
  <title>Ice vs. hydrate</title>
      <p>The impact of phase competition between ice and
hydrate is shown in Fig. 8. In the base scenario (Fig. 8a and c) hydrate
stability is excluded from the permafrost zone as described in
Text S3. Preventing ice from forming in an altered-physics simulation (<inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>
No Ice) decreases the fluid-phase salinity relative to the base simulation
and allows the methane hydrate stability zone to nearly reach the sea floor
(Fig. 8b and d) during strongest glacial conditions. Another
altered-physics simulation was done, in which ice is allowed to form but not
to affect the salinity as it drives methane hydrate stability (which was
hardwired to marine salinity). Methane hydrate is still unstable in the
permafrost zone through most of the simulation (see movie files in
the Supplement), indicating that thermal interaction must also have a
strong impact on methane hydrate stability in the permafrost zone.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8"><caption><p>Sensitivities of the hydrate stability zone. Impact of the
competition between ice and hydrate phases <bold>(a–d)</bold>, and the geothermal
temperature gradient <bold>(e–f)</bold>. When ice is included as a potential solid phase,
the pore waters are salty in the permafrost zone <bold>(a)</bold>, restricting hydrate
stability to at least 300 m below sea level throughout the simulation <bold>(c)</bold>. When ice is forbidden to form, hydrate can be stable nearly to the
sediment surface during the height of the glaciation <bold>(b)</bold> and <bold>(d)</bold>. The base of
the stability zone is sensitive to the geothermal temperature gradient,
while the shallowest reach of the stability zone does not respond to
changing heat fluxes because the temperatures are “anchored” at the ocean
value at the top of the sediment column.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f08.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SSx2" specific-use="unnumbered">
  <title>Dissolved methane</title>
      <p>The evolution of the dissolved methane
disequilibrium condition (CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mtext>4sat</mml:mtext></mml:msub></mml:math></inline-formula>) is shown in Fig. 9.
At the initiation of the glacial cycles, methane is undersaturated in
near-surface sediments on the continental shelf by diffusive contact with
the methane-free ocean upper boundary condition. In the prefreshened
sediment column scenario (Fr), methane concentrations in the depth range of
100–1000 m are lower than in the marine case (Mr, Fig. 9b) due to
the ventilation by the hydrological pump (Fig. 9a). Further freshening of
the pore waters in the ice-free case (SL <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>L D) tends to deplete methane in
the upper sediment column (Fig. 9c–e), while methane exclusion from the
permafrost ice leads to supersaturation in simulation GL <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> LD (Fig. 9f–h).
The hydrate stability zone is somewhat expanded in the prefreshened sediment
column relative to the marine case (Fig. 9g vs. h, heavy black contour).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F9" specific-use="star"><caption><p>Dissolved methane concentration relative to equilibrium (<inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Ω</mml:mi><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> CH<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub><mml:mspace width="0.125em" linebreak="nobreak"/></mml:mrow></mml:math></inline-formula>/<inline-formula><mml:math display="inline"><mml:mspace linebreak="nobreak" width="0.125em"/></mml:math></inline-formula>CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">4</mml:mn><mml:mo>(</mml:mo><mml:mi mathvariant="normal">sat</mml:mi><mml:mo>)</mml:mo></mml:mrow></mml:msub></mml:math></inline-formula>). Solid contours indicate ice fraction;
dashed contours show the methane hydrate stability boundary. Movies for the left,
center, and right columns, respectively, can be seen at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig9a.movie.gif</uri>,
<uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig9b.movie.gif</uri>, and <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig9c.movie.gif</uri>.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f09.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SSx3" specific-use="unnumbered">
  <title>Methane sources</title>
      <p>Figure 10 shows snapshot sections of various
aspects of the shelf carbon cycle, beginning from a prefreshened initial
condition. Sections of POC concentration in Fig. 10, left, show the
accumulation of POC-rich Yedoma deposits on land (Fig. 10g and j). The
rate of methane production in the model (Fig. 10, right) depends on
temperature and organic-carbon age, but it is also attenuated by permafrost
formation in the model, scaling to 0 in the completely frozen case.
Methanogenesis rates are near 0 in the permafrost zone during glacial
times (Fig. 10h) but partially recover during interglacial times (Fig. 10k) even though permafrost is still present.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F10"><caption><p>Carbon cycle through glacial cycles from a prefreshened initial
condition. Solid contours: ice fraction. Dashed contours: methane hydrate
stability zone. Left: particulate organic carbon (POC) concentration (“wt” stands for “weight”). Movie
at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig10a.movie.gif</uri>. Center: biological
methane production rate. Movie at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig10b.movie.gif</uri>. Right: methane
hydrate concentration. Movie at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig10c.movie.gif</uri>. Movies of methane hydrate stability and
concentration are given for the sensitivity studies in Supplement and at
<uri>http://geosci.uchicago.edu/~archer/spongebob/</uri>.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f10.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SSx4" specific-use="unnumbered">
  <title>Hydrate</title>
      <p>A zone of methane hydrate stability exists below the
permafrost zone when permafrost is present, and some methane hydrate
accumulates in that zone. The highest pore-fraction values are found near
the continental slope, where the shelf stability field outcrops within the
slope depocenter. Dissolved methane concentrations exceed saturation within
the stability zone in the model (Fig. 9), but the accumulation of methane
hydrate (Fig. 10, right) is limited by the rate of methane production.</p>
      <p>Time series plots of the inventory of methane as hydrate on the shelf are
shown in Fig. 11. The integration cuts off at <inline-formula><mml:math display="inline"><mml:mrow><mml:mi>x</mml:mi><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> 560 km to exclude the
sediment depocenter on the continental slope. Hydrate inventories reach
maximum values during deglaciations. There is more hydrate when the pore
water is fresher, and there would be more if ice were prevented from forming
(Fig. 11a). The hydrate inventory is much more sensitive to thermogenic
methane production, deep in the sediment column, than Yedoma deposition
(Fig. 11b). The impact of the geothermal heat flux is to change the depth
of the bottom of the hydrate stability zone (Fig. 18e and f), but the
impact is small on the hydrate inventory, unless the temperature gradient is
so low that hydrate persists through the entire glacial cycle (Fig. 11c).
The hydrate forms from the dissolved methane pool, which exceeds 1000 Gton C
in shelf pore waters of the model.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F11"><caption><p>Glacial cycle of methane hydrate inventory on the continental
shelf. <bold>(a)</bold> Effects of salt and ice. <bold>(b)</bold> Sensitivity to methanogenesis rates.
<bold>(c)</bold> Sensitivity to the column temperature gradient. <bold>(d)</bold> Glacial cycles of
shelf bubble inventories, and effects of salt and ice.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f11.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SSx5" specific-use="unnumbered">
  <title>Permafrost, ocean, and atmospheric methane flux</title>
      <p>The impact of the
glacial cycles on the methane pathway to the atmosphere in the model is
shown in Fig. 12. When sea level is high, the efficiency with which bubbles that escape the sediment reach the atmosphere ranges
from about 75 % near the coast to about 10 % at the shelf break
(Fig. 12a). Most of the methane flux from the sediment is located just off the
shelf break (Fig. 12e), where the escape efficiency is low, so not much
methane makes it to the atmosphere during the interglacial. During glacial
times, the sediment column is exposed to the atmosphere, and the escape
efficiency in the model is 100 % (Fig. 12b). Permafrost inhibits the
terrestrial methane flux (Fig. 12i) relative to the case without
permafrost (Fig. 12f). During some deglaciations, the release of pent-up
gas by permafrost degradation leads to a spike of excess methane flux to the
atmosphere (Fig. 12j–k relative to g–h).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F12" specific-use="star"><caption><p>Spatial distribution and sea level impact of methane fluxes to
the atmosphere. Panels <bold>(a–d)</bold>: solid line shows the elevation of the sediment surface
relative to the sea level at the time. Blue lines (scale to right) show the
efficiency of bubble transport through the water column, assuming a flux
attenuation length scale of 30 m. Red lines show the batymetry. Panels <bold>(e–k)</bold>: dashed blue line: methane bubble flux
across the sediment surface. Solid red line: methane bubble flux to the
atmosphere (dashed line multiplied by transport efficiency). Most of the
methane flux in the model occurs near the shelf break, and submergence in
the ocean has a strong impact on the flux to the atmosphere. A related movie
can be seen at
<uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/fig12.movie.gif</uri>.</p></caption>
          <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f12.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SSx6" specific-use="unnumbered">
  <title>Budget</title>
      <p>Time series plots of the major fluxes of the methane cycle on
the continental margin are shown in Fig. 13. The methanogenesis rates in
the model output are in units of moles per meter of coastline, since it is a
two-dimensional model. We scale this up to the Siberian continent (<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:mn>11</mml:mn></mml:msup></mml:math></inline-formula> m<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula>),
roughly comparable to the real shelf area of 460 000 km<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> (Stein and Fahl, 2000).
The biological rate of methane production on the continental shelf evolves
through time in Fig. 13b. Yedoma deposition (case SL <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> LD) tends to slowly
increase the total shelf respiration rate in the model, relative to a case
with no land deposition (case SL). The formation of permafrost, during
glacial periods of case GL <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> LD, attenuates methanogenesis by inhibiting
biological activity in the frozen soil.</p>
      <p>The solid regions in Fig. 13c–h are cumulative methane sinks for six
different model scenarios, plotted underneath red lines showing biogenic
methane production. In time average, where sinks balance sources, the
colored areas should fill up the region below the red line.</p>
      <p>The trapping of methane by impermeable permafrost leads to a spike of methane
fluxes at the ends of deglaciations in simulations with permafrost (Fig. 13c and e). The spikes happen as sea level approaches its highest extent,
stifling the offshore groundwater flow by decreasing the pressure head, but
they occur early in the interglacial period while permafrost is the most intact. The
spikes are stronger for the first glacial cycles than the last, apparently
due to long-term adjustment of the methane cycle on the shelf (a convergence of the production rate (red lines in Fig. 13c–f) and the various
methane sinks (colored areas)).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F13"><caption><p>Glacial–interglacial cycle of methane fluxes on the continental
margin of the model. Sea level is shown at top, with grey regions indicating interglacial
intervals and pink the Anthropocene. <bold>(a–e)</bold> Cumulative methane fluxes. Red lines
show production rate. Brown regions show lateral transport of dissolved
methane. Grey shows oxidation by 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> in the sediment column.
Blue shows bubble flux to the water column. During interglacial times (e.g.,
far left) there is a small onshore transport of methane, which is
represented by a negative starting point for the oxidation (grey) region. In
equilibrium, the colored areas should fill in the area under the red
curve.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f13.pdf"/>

        </fig>

      <p>Permafrost formation blocks methane emission during times of low sea level.
This can be seen in the collapse of the blue regions in Fig. 13c vs. d
and e vs. f during times of low sea level. Blocking horizontal flow disrupts
offshore flow, the only significant methane sink on the shelf during glacial
periods (Fig. 13h), resulting in somewhat higher deglacial spikes of
methane emission than predicted by the models including transport. There is
no direct link between ice fraction and methane oxidation in the model,
which is driven only by coexisting concentrations of sulfate and methane,
but the rate of methane oxidation also drops to negligible levels during glacial
times in the simulations with permafrost (grey in Fig. 13c and e). The
absolute rates of methane loss differ between the prefreshened vs. marine
initial conditions, but this is in part due to differences in the width of
the continental shelf between the two simulations. The patterns of the
methane cycle are very similar, however, between the two cases and are also not
much affected by the imposition of permeable vertical channels (Fig. 13g).</p>
</sec>
<sec id="Ch1.S3.SSx7" specific-use="unnumbered">
  <title>Atmospheric flux</title>
      <p>Fluxes of methane to the atmosphere are shown in
Fig. 14. In the absence of permafrost (Fig. 14a and b), or assuming
that bubble migration is blocked only if the ice fraction exceeds 90 %, a
condition rarely attained in the model (Fig. 14e), the highest methane
fluxes to the atmosphere are found during glacial (cold) times rather than
warm interglacials. This is due to the dissolution of methane gas into the ocean
when the sediment column is submerged. When permafrost blocks methane gas
fluxes in the sediment column, the highest atmospheric fluxes are generally
found during the time of early sea level fall, when unfrozen sediment is
exposed to the atmosphere before it has a chance to freeze. The timing of
the variations in atmospheric flux through the glacial cycles is very
sensitive to the critical ice fraction for blocking gas transport (Fig. 14e).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F14"><caption><p>Methane fluxes to the atmosphere. Sea level is shown at the top,
with interglacial intervals displayed as vertical grey bars and the Anthropocene in pink.
Panel <bold>(a)</bold> shows methane fluxes from a prefreshened initial condition, with and without permafrost
formation. Panel <bold>(b)</bold> shows methane fluxes from a pure marine initial condition. Panels <bold>(c)</bold> and <bold>(d)</bold> show sensitivity to
terrestrial organic-carbon deposition as stands during low sea level and to
thermogenic methane flux. Panel <bold>(e)</bold> shows sensitivity to the impact of the ice fraction on
bubble mobility.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f14.pdf"/>

        </fig>

      <p>The impacts of the pore water salt inventory are most apparent during the
time of sea level fall, with permafrost formation (red lines). The saltier
sediment column takes about 20 kyr to choke off the methane flux to the
atmosphere (Fig. 14a), while the prefreshened sediment column stops the
methane flux more abruptly, in just a few thousand years (Fig. 14b).
Atmospheric emissions also scale with methane production rates, generally
maintaining the temporal patterns of emission as set by permafrost and
submergence in the ocean.</p>
</sec>
<sec id="Ch1.S3.SS2">
  <title>Anthropogenic global warming</title>
      <p>The atmospheric methane fluxes, shown in Fig. 15, increase in the global
warming (GW) model run, as they also do in the control (Ctl) simulation,
which is essentially an extended but unwarmed interglacial period. The
permafrost melts on a timescale of about 10 000 years for the GW
simulation, and about 50 000 for the Ctl. The rates of methane production
and flux to the atmosphere both increase with the loss of the permafrost,
if there is no change in sea level. However, the new methane flux comes not
as a sudden burst but rather as a slow transition toward a new, higher,
chronic release rate.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F15"><caption><p>Impact of anthropogenic warming on the methane cycle in the
model. Panel <bold>(a)</bold> shows base cases: a warming scenario (GW), without and with a geological
timescale sea level rise scenario (<inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>SLR), and extended interglacial
control (Ctl). Warming plus increasing sea level decreases the methane flux
overall, due to bubble dissolution in a deeper water column. Panel <bold>(b)</bold> shows altered
model physics impacts. Panels <bold>(c)</bold> and <bold>(d)</bold> show altered methanogenesis rates. Panel <bold>(e)</bold> shows the sensitivity
to the ice fraction at which bubble mobility is assumed to be stopped.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f15.pdf"/>

        </fig>

      <p>When sea level is also changed (GW <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> SL), bubbles dissolve in the water
column, which more than counteracts the increase in methane flux due to the
extended interglacial (Ctl) or warming (GW) scenarios.</p>
</sec>
<sec id="Ch1.S3.SS3">
  <title>Sensitivity studies</title>
<sec id="Ch1.S3.SS3.SSS1">
  <title>Sediment salt content</title>
      <p>Ice freezes until the salinity of the residual brine brings about a freezing
point depression equal to the in situ temperature. A saltier initial
sediment column will reach this condition with a lower ice fraction, its
melting is accelerated, and its hydrate inventory is lower (Fig. 14). The
equilibrium salinity in the permafrost zone is not affected by the salt
inventory of the column, only the relative volumes of the solid and fluid
phases.</p>
</sec>
<sec id="Ch1.S3.SS3.SSS2">
  <title>Methane production rates</title>
      <p>The atmospheric flux increases along with either shallow, biological methane
production, driven by deposition of Yedoma, or thermal methane production in
the deep sediment column (Fig. 15). Biogenic methane production is too
shallow in the sediment column to impact the inventory of methane hydrate
(Fig. 11). The timings through the glacial cycles of atmospheric methane
emissions from these scenarios parallel each other because they are
controlled in common by the transport-blocking effects of permafrost and
sediment submergence in the ocean.</p>
</sec>
<sec id="Ch1.S3.SS3.SSS3">
  <title>Geothermal temperature gradient</title>
      <p>When the heat flux is higher, the temperature gradient is steeper, pivoting
about the sediment surface temperature, which is set by the ocean. The base
of the methane hydrate stability boundary becomes shallower, while the top
remains at about the same depth, resulting in a thinning of the stability
zone (Fig. 8). The hydrate inventory through the glacial cycles, however, is
not much affected, unless the heat flux becomes small enough for hydrate to
persist through the glaciations (Fig. 11).</p>
</sec>
<sec id="Ch1.S3.SS3.SSS4">
  <title>Thermodynamic competition between ice and hydrate</title>
      <p>When ice is included as a competing phase, it excludes methane hydrate from
the low-pressure, very cold permafrost zone. The hydrate stability zone
thins (from above and below in the model: Fig. 8), and the hydrate
inventory decreases (Fig. 11). When ice formation is disallowed, the
hydrate stability zone approaches the sediment surface during coldest
glacial times, but by the time of an interglacially based global warming
climate perturbation, the stability zone boundary has retreated to several
hundred meters below the sea floor, precluding a sudden hydrate dissolution
response to a suddenly warming ocean.</p>
      <p>When the ice fraction of the model exceeds a critical threshold, gas
migration is blocked. Changing the value of this threshold has a strong
impact on the rates of methane emission during glacial versus interglacial
times. This process is therefore a high priority for future model
refinement.</p>
</sec>
<sec id="Ch1.S3.SS3.SSS5">
  <title>Vertical flow heterogeneity</title>
      <p>The chemistry of continental-margin sediments in this model (Archer et al., 2012)
showed a strong sensitivity to flow heterogeneity, achieved by increasing
the vertical permeability of every fifth grid cell. In the configuration
presented here, the impact of the channels is much smaller. The dynamics of
this simulation are thermally driven, rather than by sediment deposition
driving fluid flow in the continental-margin case. Atmospheric methane
fluxes are spikier when the channels are included, but the mean rate is not
much changed.</p>
</sec>
<sec id="Ch1.S3.SS3.SSS6">
  <title>Groundwater flow</title>
      <p>Groundwater flow carries enough methane to be a significant sink during
times of low sea level. However, disabling that flow has only subtle impacts
on the other aspects of the methane cycle on the shelf. Spikes of methane
emission during late deglaciation become somewhat more intense.</p>
</sec>
</sec>
<sec id="Ch1.S3.SS4">
  <title>Comparison with observations</title>
      <p>The model bubble flux to the atmosphere in the base case in analog
present-day conditions is 0.02 Tg CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> per year, which is an order of
magnitude lower than an estimate of the total methane emission rate from the
sea surface (bubbles <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> gas exchange; Kort et al., 2012) of
0.3 Tg CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> yr<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>. The model does not include gas exchange evasion of
methane from the sea surface, which could be significant. Concentrations of
methane in the water column of 50 nM are common (Shakhova et al., 2010a); if they
were unimpeded by sea ice, they could lead to a flux of 0.4 Tg CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> yr<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> from the region (assuming a typical gas exchange piston velocity of 3 m 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>).
Gas exchange is impeded by sea ice, but it can be enhanced by storms
(Shakhova et al., 2013). Once released to the water column, the fate of a
methane molecule will depend on its lifetime with respect to oxidation,
which could be up to a year in the open-water column (Valentine et al., 2001),
versus its lifetime with respect to gas exchange, which for ice-unimpeded
conditions would be just a few months for a 50 m deep water column. Thus,
the methane in bubbles dissolving in the water column has some chance of
making it to the atmosphere anyway, depending on stratification in the water
column and the extent of ice, and the gas exchange flux has the potential to
be significant in the regional total flux.</p>
      <p>Methane fluxes into the water column range up to 0.4 Tg CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> yr<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> during
times of relatively high sea level. This is much lower than the Shakhova et al. (2013) estimate of 17 Tg CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:math></inline-formula> yr<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> from hot-spot
ebullition fluxes to the water column. The model fluxes are comparable to
these observations when the thermal methane flux is increased by a factor of
100 (see Sect. 3.3.2), but the model lacks the physical or mechanistic
detail required to focus the emissions into hot spots of concentrated
methane flux as observed (Sect. 4.1).</p>
</sec>
</sec>
<sec id="Ch1.S4" sec-type="conclusions">
  <title>Discussion</title>
<sec id="Ch1.S4.SS1">
  <title>Limitations of the model results and critical issues for future
development</title>
      <p>This is the first simulation of the full methane cycle on the Siberian
continental margin, or any other location with embedded permafrost soils,
including hydrate formation and transient fluxes. It is internally
consistent, linking processes from the ocean, the sea floor, and the deep
Earth, within constraints of sediment accommodation and conservation of
carbon, through geologic time. As such it has some lessons to teach about
the real Siberian continental margin. However, many of the model variables
are not well known, such as the methanogenesis rates or soil
permeabilities, meaning that in some aspects the model results are not a
strong constraint on reality. These uncertainties illuminate critical issues
for future model refinement.</p>
<sec id="Ch1.S4.SS1.SSS1">
  <title>Methane production rates</title>
      <p>The rates of biological and thermal methane production on the Siberian
continental shelf are not well constrained by laboratory measurements or
field inferences. These rates are treated as tunable model parameters, and
the sensitivity studies show that they are important ones to ultimately get
right.</p>
</sec>
<sec id="Ch1.S4.SS1.SSS2">
  <title>Gas transport in the sediment column</title>
      <p>Simulating the hot-spot behavior of bubble emission from the sea floor will
also require more detailed treatment of the mechanisms by which gas moves
around in the sediment column. The model lacks faults and permeable layers
that act as transport highways and hydrate depocenters and may concentrate
the flow into a hot-spot ebullition region. The model also lacks the ability
to episodically “blow out”, producing the sedimentary wipe-out zones
observed seismically in the subsurface (Riedel et al., 2002) and the pockmarks
at the sediment surface (Hill et al., 2004). The steady-state hydrate
inventory in the model is extremely sensitive to the bubble vertical
transport spatial scale (Archer et al., 2012), which determines how far a bubble
can get through unsaturated conditions before it redissolves. This result
demonstrates the importance of gas transport to predicting the methane
hydrate or bubble inventories.</p>
</sec>
<sec id="Ch1.S4.SS1.SSS3">
  <title>Atmospheric flux efficiency</title>
      <p>On land, the model lacks seasonal melting of surface permafrost and the
thaw bulbs underneath lakes and rivers. In the ocean, the fraction of the
bubbles which dissolves in the water column depends on the bubble sizes, which
depend on the gas emission rate, ultimately driven by details of gas
transport in the sediment.</p>
</sec>
<sec id="Ch1.S4.SS1.SSS4">
  <title>Uncertainty in model output</title>
      <p>These uncertainties affect the flux of methane to the atmosphere and model
predictions of the standing stocks of methane as gas and hydrate in the
sediment column.</p>
</sec>
</sec>
<sec id="Ch1.S4.SS2">
  <title>Robust features of the simulation</title>
<sec id="Ch1.S4.SS2.SSS1">
  <title>Arctic Ocean methane fluxes are small in the global budget</title>
      <p>The model is consistent with observations (Kort et al., 2012),
that the total atmospheric methane flux from the Siberian margin is a small
fraction of the global flux of methane to the atmosphere and thus
represents only a minor climate forcing. The model would have to be pushed
very hard (as would the measurements) to fundamentally change this
conclusion.</p>
</sec>
<sec id="Ch1.S4.SS2.SSS2">
  <title>The hydrological salinity ratchet</title>
      <p>Groundwater flow, driven by the pressure head, provides an advective means
of pumping freshwater into the subsurface sediment column that has no
counterpart for salty ocean water. The model lacks the mechanism of salt
fingering, which can enhance the diffusion of salt from above into a freshwater aquifer (Kooi et al., 2000). However, higher-resolution models of smaller
domains that accounted for salt fingering also show a time asymmetry, with
faster freshwater invasion on sea level drop than salt invasion on sea
level rise (Lu and Werner, 2013; Watson et al., 2010). As the size of the domain increases
with increasing sea level change, advective processes such as hydrological
flow should become even more dominant over diffusive processes such as salt
fingering. The recent discovery of vast freshwater aquifers on global
continental shelves (Post et al., 2013), persisting since the time of
lowered sea level 20 000 years ago, and the lower-than-marine salinities of
the pore waters measured in submerged surface Arctic sediments (summarized
by Nicolsky et al., 2012) are also consistent with the existence of a
fresh-water hydrological pump which has a significant impact on sediment
column salinities.</p>
</sec>
<sec id="Ch1.S4.SS2.SSS3">
  <title>Salinity (water activity) and hydrate stability in the permafrost zone</title>
      <p>In the simulations the pore water salinities in the permafrost zone did not
depend on the total salt content of the sediment column but only on the
temperature (and secondarily on the pressure). A saltier sediment column
will end up with a larger volume of brine in equilibrium than a fresher
sediment column would have, but the salinities of the brines would be the
same.</p>
      <p>In the permafrost zone (low temperature and pressure), ice can tolerate
higher salinity (lower water activity) than methane hydrate can. As long as
there is no kinetic impediment to ice formation, bubbles of methane rising
into this zone should encounter brine salinities too high to permit the formation of methane hydrate (Sect. A3).</p>
</sec>
<sec id="Ch1.S4.SS2.SSS4">
  <title>Sea level dominates the glacial cycle of methane flux</title>
      <p>The methane flux to the atmosphere through the glacial–interglacial cycles
is highest during cold times because sea level is low, and it contrasts with the positive feedback response of releasing methane during warm (high
sea level) intervals. Atmospheric methane concentrations were lower during
glacial times than interglacials, but since the Arctic Ocean is a small
fraction of the total methane budget (Sect. 4.2.1), the atmospheric
concentration does not necessarily reflect Arctic fluxes.</p>
</sec>
<sec id="Ch1.S4.SS2.SSS5">
  <title>Methane emission response to anthropogenic climate change</title>
      <p>There is a warming positive feedback in the simulated future from climate
warming, with fluxes rising gradually on a timescale of thousands of years.
Shakhova et al. (2010b) proposed that 50 Gton C as methane could erupt
from the Arctic on a timescale of a few years. However, the thermodynamic
exclusion of methane hydrate from the permafrost zone (Sect. 4.2.2)
ensures that methane hydrate will be isolated from changes in ocean
temperature by <inline-formula><mml:math display="inline"><mml:mo>∼</mml:mo></mml:math></inline-formula> 400 m of mud and ice. A warming
perturbation at the sea floor today will not reach this depth for hundreds
or thousands of years. A complex model is not really required to conclude
that methane hydrate will probably not produce a methane eruption of this
scale so quickly.</p>
      <p>Could an abrupt methane release arise from the release of trapped bubbles from
melting ice? The model actually does produce a glacial cycle in bubble
inventory, with changes exceeding 50 Gton over a cycle, apparently driven by
methane exclusion from ice formation (Fig. 11). However, the model does not
deliver an abrupt release in response to anthropogenic warming for any of
its sensitivity studies (Fig. 14). We would get a faster initial response
to global warming if the transition from glacial to global warming sediment
surface temperatures had not mostly happened thousands of years ago.</p>
      <p><?xmltex \hack{\newpage}?>The model provides a poor constraint on the standing stock of bubbles or
methane hydrate in the sediment column and neglects many of the mechanisms
that could come into play in transporting methane quickly to the atmosphere,
such as faults, channels, and blowouts of the sediment column. A continuum
model such as this one predicts a smooth methane release response to a
warming, growing on some <inline-formula><mml:math display="inline"><mml:mi>e</mml:mi></mml:math></inline-formula>-folding timescale. A world dominated by
features that each represent a small fraction of the total methane reservoir
will release methane more episodically, but the statistical distribution of
the response in time should still show the <inline-formula><mml:math display="inline"><mml:mi>e</mml:mi></mml:math></inline-formula>-folding timescale of the
underlying driving mechanism, the diffusion of heat into the sediment
column.</p>
      <p>The way to deliver 50 Gton of methane to the atmosphere on a short timescale is for it all to be released from a single geologic feature pent-up by
ice. However, 50 Gton of C represents a large fraction of all the traditional
natural gas deposits on Earth (about 100 Gton C). The place to look for such
a large unstable gas reservoir is in the field, not in this model, but until
such a thing is found it remains conjecture.</p>
      <p>On timescales of thousands of years and longer, carbon from deep methane
hydrates and frozen organics on the Siberian continental shelf could reach
the atmosphere–ocean carbon cycle, potentially significantly amplifying
the “long-tail” climate impact of anthropogenic carbon release. Methane
that is oxidized in the ocean would eventually equilibrate with the
atmosphere, so it is much easier for escaping methane to impact the long
tail as CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> than it is to affect the near future as methane.</p>
      <p>The potential for future sea level change is much higher on millennial timescales than the forecast for the year 2100 because it takes longer than a
century for ice sheets to respond to changes in climate. The model finds
that for the future, if sea level changes by tens of meters, as indicated by
paleoclimate reconstructions (Archer and Brovkin, 2008), the impact of sea level rise could
overwhelm the impact of warming. The dominance of sea level over temperature
in the model of this area is due to the dissolution of methane in the water
column rather than a pressure effect on hydrate stability, which is
generally a weaker driver than ocean temperature in deeper-water settings
(Mienert et al., 2005).</p><?xmltex \hack{\clearpage}?>
</sec>
</sec>
</sec>

      
      </body>
    <back><app-group><app id="App1.Ch1.S1">
  <title/>
<sec id="App1.Ch1.S1.SS1">
  <title>Vertical flow</title>
      <p>In previous versions of the SpongeBOB model, the fluid flow was calculated
explicitly, at each time step, as a function of <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> at the beginning
of the time step. Numerical stability motivated a modification of the
vertical flow to an implicit numerical scheme, which finds, by iteration, an
internally consistent array of vertical flow velocities and resulting
<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>P</mml:mi><mml:mi mathvariant="normal">excess</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> values from a time point at the end of the time step. Ocean and
atmosphere models often use this methodology for vertical flow. A benefit of
this change is stability in the vertical flow field, reducing numerical
noise that can cause trouble with other aspects of the model, such as ice
formation. Implicit schemes can be more efficient computationally, but in
this case just the stability, and not the execution time, is improved by the implicit method.</p>
      <p>Note that the flow scheme in its formulation is entirely elastic, whereas in
reality, pore fluid excluded by the pressure of a sediment column above sea
level, for example, where it is uncompensated for by buoyancy in seawater,
should remain excluded when sea level rises again, like toothpaste from the
tube. However, my attempts to embed this plastic behavior into an implicit
solver failed to converge.</p>

      <?xmltex \floatpos{t}?><fig id="App1.Ch1.F1"><caption><p>Thermodynamics of hydrate and ice. (Top) Colors are salinities,
which range from fresh if there is no solid phase to saltier as the
freezing point depression of the solid phase follows the in situ
temperature. Contours indicate the extent of thermal disequilibrium, <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>.
Panel <bold>(a)</bold> shows the thermodynamics for the system of ice and fluid. Panel <bold>(b)</bold> considers hydrate and fluid phases, excluding ice formation and assuming
equilibrium with methane gas. Panel <bold>(c)</bold> shows combined ice <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> hydrate <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> fluid system,
where the salinity is controlled by the most stable solid phase. Solid
contours are <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq,  hydrate</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, dashed <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq, 
ice</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>. In panels <bold>(d)</bold> and <bold>(e)</bold> colors are <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, where 0 (purple) indicates stability,
and contours are the excess salinity relative to a solid phase, e.g.,
<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">max</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi>S</mml:mi><mml:mrow><mml:mi mathvariant="normal">eq</mml:mi><mml:mo>,</mml:mo><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">hydrate</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:math></inline-formula> in <bold>(d)</bold> for hydrate and <bold>(e)</bold> for ice. Panel <bold>(f)</bold> shows a phase
diagram for the ice <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> hydrate <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> brine system. Hydrate is excluded from
the ice phase space by the high salinity of the brine. Ice is ideally also
excluded from part of the hydrate stability zone by a similar mechanism, but
this would only happen in nature under conditions of unlimited methane
availability. Thus, it is easier to envision coexistence of hydrate and ice
within the hydrate stability zone, under conditions of limited methane
availability, than it is to imagine hydrate in the permafrost zone, where
ice has no impediment to formation.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f16.pdf"/>

        </fig>

</sec>
<sec id="App1.Ch1.S1.SS2">
  <title>Ice formation</title>
      <p>The ice content in a grid cell relaxes toward equilibrium, quickly enough to
approximate an equilibrium state through the slow temperature evolution in
the model (which neglects a seasonal cycle at the surface) but slowly
enough to avoid instabilities with other components of the model such as
fluid flow and methane hydrate formation. A limiter in the code prevents
more than 99 % of the fluid in a grid cell from freezing, but the
thermodynamic equilibrium salinity is used to calculate, for example, the
stability of methane hydrate, to prevent the numerical limiter from
affecting the thermodynamic availability of water to drive chemical
reactions.</p>
</sec>
<sec id="App1.Ch1.S1.SS3">
  <title>Thermodynamics of ice and hydrate</title>
      <p>When the system consists only of ice and fluid phases, the equilibrium
salinity <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> increases with decreasing temperature below freezing
(Fig. A1a, left). Above the melting temperature, ice is unstable, as
indicated by the nonzero values of the disequilibrium temperature, <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq,  ice</mml:mtext></mml:msub><mml:mo>=</mml:mo><mml:mi>T</mml:mi><mml:mo>-</mml:mo><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq,  ice</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>, in contours, even in
zero-salinity water (right). For a system consisting of only the hydrate and
fluid phases (assuming that gas saturation for methane and ice formation is disallowed; Fig. A1b), the behavior is similar but with an
added pressure dependence due to the compressibility of the gas phase.</p>
      <p>When both solid phases are allowed, the overall equilibrium salinity
will be whichever is higher between <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mtext>eq,  ice</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mtext>eq  hydrate</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>.
Whichever phase can seize water at its lowest activity (highest salinity)
will be the stable phase. The salinity of the brine excluded from that phase
will be too high to permit the existence of the other solid phase at that
temperature. The contours show <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> for hydrate (solid) and ice
(dashed), which are also plotted in color in Fig. A1d and e. This is
illustrated in Fig. A1d, in colors of <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq,  hydrate</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> and
contours of the excess salinity relative to hydrate equilibrium, <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mi mathvariant="normal">max</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
– <inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi>S</mml:mi><mml:mtext>eq,  hydrate</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula>. Hydrate is only stable when <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq, hydrate</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is 0 (purple color).</p>
      <p>Under permafrost conditions of low pressure and low temperature (upper left
corner), <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Δ</mml:mi><mml:msub><mml:mi>T</mml:mi><mml:mtext>eq,  hydrate</mml:mtext></mml:msub></mml:mrow></mml:math></inline-formula> is greater than 0, indicating that
hydrate is unstable and coinciding with the salinity forcing from the ice (in
overlain contours). A similar exclusion of ice in part of the hydrate
stability zone is seen in Fig. A1e, but this would only happen in nature in
conditions of unlimited methane. The resulting phase diagram for ice and
methane hydrate is shown in Fig. A1f. Hydrate stability is suppressed in
the permafrost zone by this thermodynamic mechanism.</p>
      <p>There is an analogous exclusion of ice from part of the methane hydrate
stability zone, but this assumes unlimited methane; if the dissolved methane
concentration is less than gas saturation, both solid phases can coexist. In
the permafrost zone, the dissolved methane concentration cannot exceed
solubility with gas saturation, so the exclusion of methane hydrate from
thermodynamic stability is inescapable.</p>
</sec>
<sec id="App1.Ch1.S1.SS4">
  <title>Construction of the prefreshened sediment column</title>
      <p>If sea level falls, exposing the sediment column to the atmosphere for the
first time, there is a pressure head gradient extending throughout the
sediment column, provoking lateral flow at all depths. As the pore fluid at
the surface is replaced by fresh runoff, the lighter density of that fluid
tends to diminish the pressure head gradient in the deeper sediment column.
The deeper pressure gradient and flow approach 0 as the freshwater lens
in the outcropping region approaches an isostatic equilibrium condition
known as the Ghyben–Herzberg relation (Moore et al., 2011), in which each meter
elevation of the water table is compensated for by about 40 m of freshwater below sea level, determined by the difference in densities of fresh
and salt water.</p>
      <p>To create this condition within the model, two simulations are presented in
which sea level was decreased by 30 and 120 m, respectively, and held
there for millions of years (Fig. A2). The 30 m drop experiment
produced land outcrop in about <inline-formula><mml:math display="inline"><mml:mrow><mml:mn mathvariant="normal">1</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:math></inline-formula> of the model domain, with the predicted
equilibrium Ghyben–Herzberg halocline reaching about 1200 m maximum
depth. The model salinity relaxes into close agreement with the predicted
halocline, lending support to the model formulation for density, pressure
head, and fluid flow. As time progresses further, the outcropping land
surface subsides (there is no land deposition in this scenario), until it
drops below the new lowered sea level value after about 2.5 Myr. The
hydrological pumping generates a low-methane plume that also persists for
millions of years in the model (Fig. A3).</p>

      <?xmltex \floatpos{t}?><fig id="App1.Ch1.F2"><caption><p>Freshening the sediment column by hydrological groundwater
flushing. Color indicates salinity. Solid black line represents sea level in
the ocean (white space), and the equilibrium Ghyben–Herzberg fresh–salty boundary given the pressure head. Left side:
results of dropping sea level by 30 m and holding it there. A freshwater
lens forms and strives to reach Ghyben–Herzberg equilibrium as the sediment
column subsides, where atmospheric exposure decreases its buoyancy and stops
sediment accumulation. After the sediment column subsides beneath the
still-lowered sea level, the freshwater lens remains for millions of years.
A movie can be seen at <uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/supp_fig2a.movie.gif</uri>. Right side: result of dropping
sea level by 120 m and holding it there forever. Movie at
<uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/supp_fig2b.movie.gif</uri>.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f17.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="App1.Ch1.F3"><caption><p>Dissolved methane impact by hydrological freshening of the
sediment column as described in Fig. A2. <inline-formula><mml:math display="inline"><mml:mrow><mml:mi mathvariant="normal">Ω</mml:mi><mml:mo>=</mml:mo></mml:mrow></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>/CH<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mtext>4(sat)</mml:mtext></mml:msub></mml:math></inline-formula>. Movies can be seen at
<uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/supp_fig3a.movie.gif</uri> and
<uri>http://geosci.uchicago.edu/~archer/spongebob_arctic/supp_fig3b.movie.gif</uri>.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f18.pdf"/>

        </fig>

      <p>Variants of this experiment were done with differing values of the lateral
distance to drainage canyons in the model, which provide a pathway for fluid
loss in sediments above sea level. When a hypothetical canyon is located 10 km from the
SpongeBOB slab, the model salinity approaches equilibrium on an
<inline-formula><mml:math display="inline"><mml:mi>e</mml:mi></mml:math></inline-formula>-folding timescale of about 400 kyr (Fig. A4). When the canyon is 100 km
distant or nonexistent, the equilibration timescale is about 600 kyr. Based
on the idea that canyons are of the order of 100 km in length should be about 100 km apart,
the base simulation in this paper assumes canyon spacing of 100 km.</p>

      <?xmltex \floatpos{t}?><fig id="App1.Ch1.F4"><caption><p>Timescale of depleting the salinity of the continental shelf
sediment column after an instantaneous sea level drop of 30 m. The
effect of lateral canyons is to provide a pathway for saline fluid to be
replaced by fresh groundwater in sediments above sea level. If the lateral
canyon spacing is 10 km, they can have a significant impact on the time
constant for groundwater flushing. A more conservative 100 km canyon is
adopted for the rest of the simulations.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://www.biogeosciences.net/12/2953/2015/bg-12-2953-2015-f19.pdf"/>

        </fig>

      <p><?xmltex \hack{\newpage}?>When sea level is lowered by 120 m, the sequence of events is similar,
except that the pressure head is so high that to satisfy the Ghyben–Herzberg
relation would require fresh pore waters at many kilometers depth, even
deeper than bedrock on the “continental” side of the model domain. Because
of the low permeability of the deepest sediment column, the freshwater-pumping groundwater mechanism is unable to reach these deepest pore waters,
which therefore remain salty. The timescale for establishing a significant
freshening of the upper kilometer of the sediment column is still on the
order of 100–500 kyr, and the subsequent subsidence time of the sediment
column in the model, until it drops below the new lowered sea level, is about 10 Myr. In both cases, subsidence of the exposed sediment column
prevents the sediment surface in the model from remaining above sea level
indefinitely (without land deposition).</p><?xmltex \hack{\clearpage}?><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-12-2953-2015-supplement" xlink:title="zip">doi:10.5194/bg-12-2953-2015-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
</sec>
</app>
  </app-group><ack><title>Acknowledgements</title><p>This paper benefited from constructive reviews by Dmitri Nicolsky and two
anonymous reviewers, comments contributed by Natalia Shakhova, Igor Semiletov, and Vladimir Tumskoy, and the efforts of the editor, Laurent Bopp.
<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?>
Edited by: L. Bopp</p></ack><ref-list>
    <title>References</title>

      <ref id="bib1.bib1"><label>1</label><mixed-citation>Archer, D. and Brovkin V.: The millennial lifetime of fossil fuel CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, Climatic Change, 90, 283–297, 2008.</mixed-citation></ref>
      <ref id="bib1.bib2"><label>2</label><mixed-citation>Archer, D. E., Buffett, B. A., and McGuire, P. C.: A two–dimensional model of the
passive coastal margin deep sedimentary carbon and methane cycles, Biogeosciences, 9, 2859–2878, <ext-link xlink:href="http://dx.doi.org/10.5194/bg-9-2859-2012" ext-link-type="DOI">10.5194/bg-9-2859-2012</ext-link>, 2012.</mixed-citation></ref>
      <ref id="bib1.bib3"><label>3</label><mixed-citation>
Archer, D. E., Eby, M., Brovkin, V., Ridgewell, A. J., Cao, L., Mikolajewicz, U.,
Caldeira, K., Matsueda, H., Munhoven, G., Montenegro, A., and Tokos, K.: Atmospheric
lifetime of fossil fuel carbon dioxide, Ann. Rev. Earth Planet Sci., 37,
117–34, 2009.</mixed-citation></ref>
      <ref id="bib1.bib4"><label>4</label><mixed-citation>
Cramer, B. and Franke, D.: Indications for an active petroleum system in the
Laptev Sea, NE Siberia, J. Petrol. Geol., 28, 369–383, 2005.</mixed-citation></ref>
      <ref id="bib1.bib5"><label>5</label><mixed-citation>
Dutta, K., Schuur, E. A. G., Neff, J. C., and Zimov S. A.:, Potential carbon release
from permafrost soils of Northeastern Siberia, Glob. Change Biol., 12, 2336–2351, 2006.</mixed-citation></ref>
      <ref id="bib1.bib6"><label>6</label><mixed-citation>
Gavrilov, A. V., Romanovskii, X. N., Romanovsky, V. E., Hubberten, H. W., and
Tumskoy, V. E.: Reconstruction of ice complex remnants on the eastern Siberian
Arctic Shelf, Permafrost Periglac., 14, 187–198, 2003.</mixed-citation></ref>
      <ref id="bib1.bib7"><label>7</label><mixed-citation>
Gentz, T., Damm, E., von Deimling, J. S., Mau, S., McGinnis, D. F., and
Schluter, M.: A water column study of methane around gas flares located at the
West Spitsbergen continental margin, Continent. Shelf Res., 72, 107–118,
2014.</mixed-citation></ref>
      <ref id="bib1.bib8"><label>8</label><mixed-citation>Hill, J. C., Driscoll, N. W., Weissel, J. K., and Goff, J. A.: Large-scale elongated
gas blowouts along the US Atlantic margin, J. Geophys.
Res.-Solid Earth, 109, B09101, <ext-link xlink:href="http://dx.doi.org/10.1029/2004JB002969" ext-link-type="DOI">10.1029/2004JB002969</ext-link>, 2004.</mixed-citation></ref>
      <ref id="bib1.bib9"><label>9</label><mixed-citation>
Hunt, J. M.: Petroleum Geochemistry and Geology, 743 pp., Freeman, New York,
1995.</mixed-citation></ref>
      <ref id="bib1.bib10"><label>10</label><mixed-citation>
Khvorostyanov, D. V., Ciais, P., Krinner,  G., Zimov, S. A., Corradi, C., and
Guggenberger, G.: Vulnerability of permafrost carbon to global warming. Part
II: sensitivity of permafrost carbon stock to global warming, Tellus
B, 60, 265–275, 2008a.</mixed-citation></ref>
      <ref id="bib1.bib11"><label>11</label><mixed-citation>
Khvorostyanov, D. V., Krinner, G., Ciais, P., Heimann, M., and Zimov, S. A.:
Vulnerability of permafrost carbon to global warming, Part I: model
description and role of heat generated by organic matter decomposition,
Tellus B, 60, 250–264, 2008b.</mixed-citation></ref>
      <ref id="bib1.bib12"><label>12</label><mixed-citation>
Kooi, H., Groen, J., and Leijnse, A.: Modes of seawater intrusion during
transgressions, Water Resour. Res., 36, 3581–3589, 2000.</mixed-citation></ref>
      <ref id="bib1.bib13"><label>13</label><mixed-citation>
Kort, E. A., Wofsy, S. C., Daube, B. C., Diao, M., Elkins, J. W., Gao, R. S.,
Hintsa, E. J., Hurst, D. F., Jimenez, R., Moore, F. L., Spackman, J. R.  and Zondlo, M.
A.:
Atmospheric observations of Arctic Ocean methane emissions up to 82 degrees
north, Nat. Geosci., 5, 318–321, 2012.</mixed-citation></ref>
      <ref id="bib1.bib14"><label>14</label><mixed-citation>
Lu, C. and Werner, A. D.: Timescales of seawater intrusion and retreat,
Adv. Water Resour., 59, 39–51, 2013.</mixed-citation></ref>
      <ref id="bib1.bib15"><label>15</label><mixed-citation>
Martin, P. A., Lea, D. W., Rosenthal, Y., Shackleton, N. J., Sarnthein, M., and
Papenfuss, T.: Quaternary deep sea temperature histories derived from benthic
foraminiferal Mg/Ca, Earth Planet. Sci. Lett., 198, 193–209,
2002.</mixed-citation></ref>
      <ref id="bib1.bib16"><label>16</label><mixed-citation>
Mienert, J., Vanneste, M., Bunz, S., Andreassen, K., Haflidason, H., and
Sejrup,  H. P.: Ocean warming and gas hydrate stability on the mid-Norwegian margin
at the Storegga Slide, Mar. Petrol.Geol., 22, 233–244, 2005.</mixed-citation></ref>
      <ref id="bib1.bib17"><label>17</label><mixed-citation>
Moore, W. S., Carlson, C. A., and Giovannoni, S. J.: The Effect of Submarine
Groundwater Discharge on the Ocean, Annual Review of Marine Science, 2,
59–88, 2011.</mixed-citation></ref>
      <ref id="bib1.bib18"><label>18</label><mixed-citation>Nicolsky, D. and Shakhova, N.: Modeling sub-sea permafrost in the East
Siberian Arctic Shelf: the Dmitry Laptev Strait, Environ. Res.
Lett., 5, 015006, <ext-link xlink:href="http://dx.doi.org/10.1088/1748-9326/5/1/015006" ext-link-type="DOI">10.1088/1748-9326/5/1/015006</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib19"><label>19</label><mixed-citation>Nicolsky, D. J., Romanovsky, V. E., Romanovskii, N. N., Kholodov, A. L.,
Shakhova, N. E., and Semiletov, I. P.: Modeling sub-sea permafrost in the East
Siberian Arctic Shelf: The Laptev Sea region, J. Geophys.
Res.-Earth Surface, 117, F03028, <ext-link xlink:href="http://dx.doi.org/10.1029/2012JF002358" ext-link-type="DOI">10.1029/2012JF002358</ext-link>, 2012.</mixed-citation></ref>
      <ref id="bib1.bib20"><label>20</label><mixed-citation>Portnov, A., Smith, A. J., Mienert, J., Cherkashov, G., Rekant, P., Semenov, P.,
Serov,  P., and Vanshtein, B.: Offshore permafrost decay and massive seabed methane
escape in water depths <inline-formula><mml:math display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn>20</mml:mn></mml:mrow></mml:math></inline-formula> m at the South Kara Sea shelf, Geophys.
Res. Lett., 40, 3962–3967, 2013.</mixed-citation></ref>
      <ref id="bib1.bib21"><label>21</label><mixed-citation>
Post, V. E. A., Groen, J., Kooi, H., Person, M., Ge, S. M., and Edmunds, W.
M.: Offshore fresh groundwater reserves as a global phenomenon, Nature, 504, 71–78, 2013.</mixed-citation></ref>
      <ref id="bib1.bib22"><label>22</label><mixed-citation>Reagan, M. T.: Dynamic response of oceanic hydrate deposits to ocean
temperature change, J. Geophys. Res.-Oceans, 113,
C12023, <ext-link xlink:href="http://dx.doi.org/10.1029/2008JC004938" ext-link-type="DOI">10.1029/2008JC004938</ext-link>, 2008.</mixed-citation></ref>
      <ref id="bib1.bib23"><label>23</label><mixed-citation>Reagan, M. T. and Moridis, G. J.: Large-scale simulation of methane hydrate
dissociation along the West Spitsbergen Margin, Geophys. Res. Lett.,
36, L23612, <ext-link xlink:href="http://dx.doi.org/10.1029/2009GL041332" ext-link-type="DOI">10.1029/2009GL041332</ext-link>, 2009.</mixed-citation></ref>
      <ref id="bib1.bib24"><label>24</label><mixed-citation>Reagan, M. T., Moridis, G. J., Elliott, S. M.,  and Maltrud, M.: Contribution of
oceanic gas hydrate dissociation to the formation of Arctic Ocean methane
plumes, J. Geophys. Res.-Oceans, 116, C09014,
<ext-link xlink:href="http://dx.doi.org/10.1029/2011JC007189" ext-link-type="DOI">10.1029/2011JC007189</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib25"><label>25</label><mixed-citation>Riedel, M., Spence, G. D., Chapman, N. R., and Hyndman, R. D.: Seismic
investigations of a vent field associated with gas hydrates, offshore
Vancouver Island, J. Geophys. Res.-Solid Earth, 107,
2200, <ext-link xlink:href="http://dx.doi.org/10.1029/2001JB000269" ext-link-type="DOI">10.1029/2001JB000269</ext-link>, 2002.</mixed-citation></ref>
      <ref id="bib1.bib26"><label>26</label><mixed-citation>
Romanovskii, N. N. and Hubberten, H. W.: Results of permafrost modelling of the
lowlands and shelf of the Laptev Sea region, Russia, Permafrost
Perigla., 12, 191–202, 2001.</mixed-citation></ref>
      <ref id="bib1.bib27"><label>27</label><mixed-citation>
Romanovskii, N. N., Hubberten, H. W., Gavrilov,  A., Tumskoy, V. E., and
Kholodov, A. L.: Permafrost of the east Siberian Arctic shelf and coastal lowlands,
Quaternary Sci. Revi., 23, 1359–1369, 2004.</mixed-citation></ref>
      <ref id="bib1.bib28"><label>28</label><mixed-citation>
Romanovskii, N. N., Hubberten, H. W.,  Gavrilov, A. V., Eliseeva, A. A., and
Tipenko, G. S.: Offshore permafrost and gas hydrate stability zone on the shelf of
East Siberian Seas, Geo-Marine Lett., 25, 167–182, 2005.</mixed-citation></ref>
      <ref id="bib1.bib29"><label>29</label><mixed-citation>
Romanovskii, N. N., Hubberten, H. W., Gavrilov, A. V., Tumskoy, V. E., Tipenko, G.
S., Grigoriev, M.N., and Siegert, C.: Thermokarst and land-ocean interactions,
Laptev Sea Region, Russia, Permafrost  Periglac., 11,
137–152, 2000.</mixed-citation></ref>
      <ref id="bib1.bib30"><label>30</label><mixed-citation>
Schuur, E. A. G., Bockheim, J.,Canadell, J. G., Euskirchen, E., Field, C. B.,
Goryachkin, S. V., Hagemann, S., Kuhry, P., Lafleur, P. M., Lee, H., Mazhitova, G.,
Nelson, F. E., Rinke, A.,  Romanovsky, V. E., Shiklomanov, N., Tarnocai, C., Venevsky,
S., Vogel, J. G., and Zimov, S. A.: Vulnerability of permafrost carbon to climate
change: Implications for the global carbon cycle, Bioscience, 58,
701–714, 2008.</mixed-citation></ref>
      <ref id="bib1.bib31"><label>31</label><mixed-citation>Shakhova, N.: Geochemical and geophysical evidence of methane release over
the East Siberian Arctic Shelf, J. Geophys. Res.-Oceans, 115, C08007,
<ext-link xlink:href="http://dx.doi.org/10.1029/2009JC005602" ext-link-type="DOI">10.1029/2009JC005602</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib32"><label>32</label><mixed-citation>Shakhova, N., Semiletov, I., Leifer, I., Sergienko, V., Salyuk, A., Kosmach,
D., Chernykn, D., Stubb, C., Nicolsky, D., Tumskoy, V. E., and Gustafsson,
O.:
Ebullition and storm-induced methane release from the East Siberian Arctic
shelf, Nat. Geosci., 7, 64–70, <ext-link xlink:href="http://dx.doi.org/10.1038/NGEO2007" ext-link-type="DOI">10.1038/NGEO2007</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib33"><label>33</label><mixed-citation>Shakhova, N., Semiletov, I., and Panteleev, G.: The distribution of methane on
the Siberian Arctic shelves: Implications for the marine methane cycle,
Geophys. Res. Lett. 32, L09601, <ext-link xlink:href="http://dx.doi.org/10.1029/2005GL022751" ext-link-type="DOI">10.1029/2005GL022751</ext-link>, 2005.</mixed-citation></ref>
      <ref id="bib1.bib34"><label>34</label><mixed-citation>
Shakhova, N., Semiletov, I., Salyuk, A., Yusupov, V., Kosmach, D., and
Gustafsson, O.: Extensive Methane Venting to the Atmosphere from Sediments of the
East Siberian Arctic Shelf, Science, 327, 1246–1250, 2010a.</mixed-citation></ref>
      <ref id="bib1.bib35"><label>35</label><mixed-citation>
Shakhova, N. E., Alekseev, V. A., and Semiletov, I. P.: Predicted methane emission
on the East Siberian shelf, Doklady Earth Sciences, 430, 190–193, 2010b.</mixed-citation></ref>
      <ref id="bib1.bib36"><label>36</label><mixed-citation>
Shakhova, N. E., Nicolsky, D. Y., and Semiletov, I. P.: Current state of subsea
permafrost on the East Siberian Shelf: Tests of modeling results based on
field observations, Doklady Earth Sciences, 429, 1518–1521, 2009.</mixed-citation></ref>
      <ref id="bib1.bib37"><label>37</label><mixed-citation>Stein, R., and Fahl, K.: Holocene accumulation of organic carbon at the Laptev
Sea continental margin (Arctic Ocean): sources, pathways, and sinks,
Geo-Mar. Lett., 20, 27–36, 2000.
 </mixed-citation></ref><?xmltex \hack{\newpage}?>
      <ref id="bib1.bib38"><label>38</label><mixed-citation>Stouffer, R. J. and Manabe, S.: Equilibrium response of thermohaline
circulation to large changes in atmospheric CO<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> concentration, Clim.
Dynamics, 20, 759–773, 2003.</mixed-citation></ref>
      <ref id="bib1.bib39"><label>39</label><mixed-citation>
Taylor, A. E., Dallimore, S. R., and Outcalt, S. I.: Late quaternary history of
the Mackenzie-Beaufort region, Arctic Canada, from modelling of permafrost
temperatures 1, The onshore offshore transition, Can. J. Earth
Sci., 33, 52–61, 1996.</mixed-citation></ref>
      <ref id="bib1.bib40"><label>40</label><mixed-citation>
Valentine, D. L., Blanton, D. C., Reeburgh, W. S., and Kastner, M.: Water column
methane oxidation adjacent to an area of active hydrate dissociation, Eel
River Basin, Geochim. Cosmochim. Ac., 65, 2633–2640, 2001.</mixed-citation></ref>
      <ref id="bib1.bib41"><label>41</label><mixed-citation>
Verrjuit, A.: A note on the Ghyben-Herzberg formula, Bull. Int. Assoc. Sci.
Hydrology, 13, 43–46, 1968.</mixed-citation></ref>
      <ref id="bib1.bib42"><label>42</label><mixed-citation>
Walter, K. M., Zimov, S. A., Chanton, J. P., Verbyla, D., and Chapin, F. S.: Methane
bubbling from Siberian thaw lakes as a positive feedback to climate warming,
Nature, 443, 71–75, 2006.</mixed-citation></ref>
      <ref id="bib1.bib43"><label>43</label><mixed-citation>Watson, T. A., Werner, A. D., and Simmons, C. T.:
Transience of seawater intrusion in response to sea level rise, Water
Resour. Res., 40, W12533, <ext-link xlink:href="http://dx.doi.org/10.1029/2010WR009564" ext-link-type="DOI">10.1029/2010WR009564</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib44"><label>44</label><mixed-citation>Westbrook, G. K., Thatcher, K. E., Rohling, E. J., Piotrowski, A. M., Paelike,
H., Osborne, A. H., Nisbet, E. G., Minshull, T. A., Lanoiselle, M., James, R. H.,
Huehnerbach, V., Green, D., Fisher, R. E., Crocker, A. J., Chabert, A., Bolton, C.,
Beszczynska-Moeller, A., Berndt, C., and Aquilina, A.: Escape of methane gas from
the seabed along the West Spitsbergen continental margin, Geophys.
Res. Lett., 36, L15608, <ext-link xlink:href="http://dx.doi.org/10.1029/2009GL039191" ext-link-type="DOI">10.1029/2009GL039191</ext-link>, 2009.</mixed-citation></ref>
      <ref id="bib1.bib45"><label>45</label><mixed-citation>Zimov, S. A., Davydov, S. P., Zimova, G. M., Davydova, A. I., Schuur, E. A. G.,
Dutta, K., and Chapin, F. S., III: Permafrost carbon: Stock and decomposability of
a globally significant carbon pool, Geophys. Res. Lett., 33,
L20502, <ext-link xlink:href="http://dx.doi.org/10.1029/2006GL027484" ext-link-type="DOI">10.1029/2006GL027484</ext-link>,
2006.</mixed-citation></ref>

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