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  <front>
    <journal-meta><journal-id journal-id-type="publisher">BG</journal-id><journal-title-group>
    <journal-title>Biogeosciences</journal-title>
    <abbrev-journal-title abbrev-type="publisher">BG</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Biogeosciences</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1726-4189</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/bg-16-3033-2019</article-id><title-group><article-title>Ideas and perspectives: is shale gas a major driver of recent increase in global atmospheric
methane?</article-title><alt-title>Shale gas and global methane</alt-title>
      </title-group><?xmltex \runningtitle{Shale gas and global methane}?><?xmltex \runningauthor{R.~W.~Howarth}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes">
          <name><surname>Howarth</surname><given-names>Robert W.</given-names></name>
          <email>howarth@cornell.edu</email>
        </contrib>
        <aff id="aff1"><institution>Department of Ecology and Evolutionary Biology, Cornell University,
Ithaca, NY 14853, USA</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Robert W. Howarth (howarth@cornell.edu)</corresp></author-notes><pub-date><day>14</day><month>August</month><year>2019</year></pub-date>
      
      <volume>16</volume>
      <issue>15</issue>
      <fpage>3033</fpage><lpage>3046</lpage>
      <history>
        <date date-type="received"><day>10</day><month>April</month><year>2019</year></date>
           <date date-type="rev-request"><day>23</day><month>April</month><year>2019</year></date>
           <date date-type="rev-recd"><day>11</day><month>July</month><year>2019</year></date>
           <date date-type="accepted"><day>12</day><month>July</month><year>2019</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2019 Robert W. Howarth</copyright-statement>
        <copyright-year>2019</copyright-year>
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019.html">This article is available from https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019.html</self-uri><self-uri xlink:href="https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019.pdf">The full text article is available as a PDF file from https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019.pdf</self-uri>
      <abstract><title>Abstract</title>
    <p id="d1e77">Methane has been rising rapidly in the atmosphere over the past
decade, contributing to global climate change. Unlike the late 20th
century when the rise in atmospheric methane was accompanied by an
enrichment in the heavier carbon stable isotope (<inline-formula><mml:math id="M1" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>) of methane,
methane in recent years has become more depleted in <inline-formula><mml:math id="M2" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>. This depletion
has been widely interpreted as indicating a primarily biogenic source for the
increased methane. Here we show that part of the change may instead be
associated with emissions from shale-gas and shale-oil development. Previous
studies have not explicitly considered shale gas, even though most of the
increase in natural gas production globally over the past decade is from
shale gas.
The methane in shale gas is somewhat depleted in <inline-formula><mml:math id="M3" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> relative to
conventional natural gas. Correcting earlier analyses for this difference,
we conclude that shale-gas production in North America over the past decade
may have contributed more than half of all of the increased emissions from
fossil fuels globally and approximately one-third of the total increased
emissions from all sources globally over the past decade.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e125">Methane is the second most important greenhouse gas behind carbon dioxide
causing global climate change, contributing approximately 1 W m<inline-formula><mml:math id="M4" 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> to
warming when indirect effects are included compared to 1.66 W m<inline-formula><mml:math id="M5" 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>
for carbon dioxide (IPCC, 2013). Unlike carbon dioxide, the climate system
responds quickly to changes in methane emissions, and reducing methane
emissions could provide an opportunity to immediately slow the rate of
global warming (Shindell et al., 2012) and perhaps meet the United Nations Framework Convention on Climate Change (UNFCCC) COP21
target of keeping the planet well below 2 <inline-formula><mml:math id="M6" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C above the pre-industrial
baseline (IPCC, 2018). Methane also contributes to the formation of
ground-level ozone, with large adverse consequences for human health and
agriculture. Considering these effects as well as climate change, Shindell (2015) estimated that the social cost of methane is 40 to 100 times greater than
that for carbon dioxide:  USD 2700 per ton for methane compared to USD 27
per ton for carbon dioxide when calculated with a 5 % discount rate and
USD 6000 per ton for methane compared to USD 150 per ton for carbon dioxide
when calculated with a 1.4 % discount rate.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1"><?xmltex \currentcnt{1}?><label>Figure 1</label><caption><p id="d1e163"><bold>(a)</bold> Global increase in atmospheric methane between 1980 and
2015. <bold>(b)</bold> Change in <inline-formula><mml:math id="M7" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> value of atmospheric methane
globally between 1980 and 2015. Both adapted from Schaefer et al. (2016).</p></caption>
        <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019-f01.png"/>

      </fig>

      <p id="d1e190">Atmospheric methane levels rose steadily during the last few decades of the
20th century before leveling off for the first decade of the 21st
century. Since 2008, however, methane concentrations have again been rising
rapidly (Fig. 1a). This increase, if it continues in coming decades, will
significantly increase global warming and undercut efforts to reach the
COP21 target (Nisbet et al., 2019). The total atmospheric flux of methane for
the period 2008–2014 was <inline-formula><mml:math id="M8" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">24.7</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year greater than for
the 2000–2007 period (Worden et al., 2017), an increase of 7 % in global
human-caused methane emissions. The change in the stable carbon <inline-formula><mml:math id="M9" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio of methane in the atmosphere over the past 35 years is
striking and seems clearly related to the change in the methane
concentration (Fig. 1b). For the final 20 years of the 20th century,
as atmospheric methane concentrations rose, the isotopic composition became
more enriched in the heavier stable isotope of carbon, <inline-formula><mml:math id="M10" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>, relative to
the lighter and more abundant isotope, <inline-formula><mml:math id="M11" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">12</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>, resulting in a less negative
<inline-formula><mml:math id="M12" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> signal. The isotopic composition remained constant from
1998 to 2008, when the atmospheric concentration was constant. And the
isotopic composition has become lighter (depleted in <inline-formula><mml:math id="M13" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>, more negative
<inline-formula><mml:math id="M14" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>) since<?pagebreak page3034?> 2009, as atmospheric methane concentrations have
been rising again (Schaefer et al., 2016; Nisbet et al., 2016). Since biogenic
sources of methane are lighter than the methane released from fossil-fuel
emissions, Schaefer et al. (2016) concluded that the increase in atmospheric
methane in the late 20th century was due to increasing emissions from
fossil fuels but that the increase in methane since 2006 is due to
biogenic sources, most likely tropical wetlands, rice culture, or animal
agriculture. Their model results indicated that fossil-fuel sources have
remained flat or decreased globally since 2006, playing no major role in the
recent atmospheric rise of methane. Schaefer et al. (2016) noted that their
conclusion contradicted many reports of increased emissions from fossil-fuel
sources over this time and stated that their conclusion was “unexpected,
given the recent boom in unconventional gas production and reported
resurgence in coal mining and the Asian economy”. Six months after the
Schaefer et al. (2016) study was published in <italic>Science</italic>, Schwietzke et al. (2016)
presented a similar analysis in <italic>Nature</italic> that used a larger and more comprehensive
data set for the <inline-formula><mml:math id="M15" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values of methane emission sources. They
too concluded that fossil-fuel emissions have likely decreased during this
century and that biogenic emissions are the probable cause of any recent
increase in global methane emissions.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><?xmltex \opttitle{Sensitivity of emission models based on {$\protect\chem{\delta^{{13}}C}$} in methane to
biomass burning}?><title>Sensitivity of emission models based on <inline-formula><mml:math id="M16" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> in methane to
biomass burning</title>
      <p id="d1e320">Model analyses that use <inline-formula><mml:math id="M17" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> methane data to infer emission
sources are highly sensitive to changes in the rate of biomass burning:
although biomass burning is a relatively small contributor to global methane
emissions, those emissions are quite enriched in <inline-formula><mml:math id="M18" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> relative to the
atmospheric methane signal (Rice et al., 2016; Sherwood et al., 2017). Both
Schaefer et al. (2016) and Schwietzke et al. (2016) assumed that biomass
burning had been constant in recent years. However, Worden et al. (2017)
estimated that biomass burning globally went down for the period 2007–2014
compared to 2001–2006, resulting in decreased methane emissions of 3.7 Tg per year (<inline-formula><mml:math id="M19" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">1.4</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year) and contributing to a lower <inline-formula><mml:math id="M20" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> for atmospheric methane. Using the data set of Schwietzke et al. (2016) for <inline-formula><mml:math id="M21" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values of methane emission sources, but
including changes in biomass burning over time, Worden et al. (2017)
concluded that the recent increase in methane emissions was likely driven
more by fossil fuels than by biogenic sources, with an increase of 16.4 Tg per year from fossil fuels (<inline-formula><mml:math id="M22" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">3.6</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year) compared to an increase
of 12 Tg per year from biogenic sources (<inline-formula><mml:math id="M23" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">2.5</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year) when
comparing 2007–2014 to 2001–2006.</p>
      <p id="d1e405">Clearly global models for partitioning methane sources based on the <inline-formula><mml:math id="M24" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> approach are sensitive to assumptions about seemingly small
terms such as decreases in biomass burning. In this paper, we explore for
the first time another assumption: that the global increase in shale-gas
development may have caused some of the depletion of <inline-formula><mml:math id="M25" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> in the global
average methane observed over the past decade. Shale-gas emissions were not
explicitly considered in the models presented by Schaefer et al. (2016) and
Worden et al. (2017) and were explicitly excluded in the analysis of
Schwietzke et al. (2016).</p>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>What is shale gas?</title>
      <p id="d1e441">Shale gas is a form of unconventional natural gas (mostly methane) held
tightly in shale-rock formations. Conventional natural gas, the dominant
form of natural gas produced during the 20th century, is composed
largely of methane that migrated upward from the underlying sources such as
shale rock over geological time, becoming trapped under a geological seal
(Fig. 2a). Until this century, shale gas was not commercially developable.
The use of a new combination of technologies in the 21st century –
high-precision directional drilling, high-volume hydraulic fracturing,<?pagebreak page3035?> and
clustered multi-well drilling pads – has changed this. In recent years,
global shale-gas production has exploded 14-fold, from 31 billion cubic meters
per year in 2005 to 435 billion cubic meters per year in 2015 (Fig. 2b), with
89 % of this production in the United States and 10 % in western Canada
(EIA, 2016). Shale gas accounted for 63 % of the total increase in natural
gas production globally over this time period (EIA, 2016; IEA, 2017). The US
Department of Energy predicts rapid further growth in shale-gas production
globally, reaching 1500 billion cubic meters per year by 2040 (EIA, 2016; Fig. 2b).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><?xmltex \currentcnt{2}?><label>Figure 2</label><caption><p id="d1e446"><bold>(a)</bold> Schematic comparing shale gas and conventional natural
gas. For conventional natural gas, methane migrates from the shale through
semipermeable formations over geological time, becoming trapped under a
geological seal. Shale gas is methane that remained in the shale formation
and is released through the combined technologies of high-precision
directional drilling and high-volume hydraulic fracturing. <bold>(b)</bold> Global production of shale gas and other forms of natural gas
from 2000 to 2017, with projections into the future from EIA (2016).
Redrawn from EIA (2016) with data from IEA (2017).</p></caption>
        <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019-f02.png"/>

      </fig>

      <p id="d1e460">Several studies have suggested that the <inline-formula><mml:math id="M26" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> signal of methane
from shale gas can often be lighter (more depleted in <inline-formula><mml:math id="M27" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>) than that
from conventional natural gas (Golding et al., 2013; Hao and Zou, 2013; Turner
et al., 2017; Botner et al., 2018). This should not be surprising. In the case
of conventional gas, the methane has migrated over geological time frames
from the shale and other source rocks through permeable strata until trapped
below a seal (Fig. 2a). During this migration, some of the methane can be
oxidized both by bacteria, perhaps using iron (III) or sulfate as the source
of the oxidizing power, and by thermochemical sulfate reduction (Whelan et al., 1986; Burruss and Laughrey, 2010; Rooze et al., 2016). This partial
oxidation fractionates the methane by preferentially consuming the lighter
<inline-formula><mml:math id="M28" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">12</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> isotope and gradually enriching the remaining methane in <inline-formula><mml:math id="M29" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> (Hao
and Zou, 2013; Baldassare et al., 2014), resulting in a <inline-formula><mml:math id="M30" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>
signal that is less negative. The methane in shales, on the other hand, is
tightly held in the highly reducing rock formation and therefore very
unlikely to have been subject to oxidation and the resulting fractionation.
The expectation, therefore, is that methane in conventional natural gas
should be heavier and less depleted in <inline-formula><mml:math id="M31" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> than the methane in shale
gas.</p>
</sec>
<sec id="Ch1.S4">
  <label>4</label><?xmltex \opttitle{Calculating the effect of {$\protect\chem{{}^{{13}}C}$} signal of shale gas on emission
sources: conceptual framework}?><title>Calculating the effect of <inline-formula><mml:math id="M32" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> signal of shale gas on emission
sources: conceptual framework</title>
      <p id="d1e559">To explore the contribution of methane emissions from shale gas, we build on
the analysis of Worden et al. (2017). Figure 3a shows the <inline-formula><mml:math id="M33" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>
values used by them as well as their mean estimates for changes in emissions
since 2008 (as they estimated using the <inline-formula><mml:math id="M34" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> data of Schwietzke
et al., 2016). Figure 3a represents a weighting for the change in emissions
(<inline-formula><mml:math id="M35" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axis) and the <inline-formula><mml:math id="M36" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values of those emissions (<inline-formula><mml:math id="M37" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axis) by
individual sources. Our addition is to separately consider shale-gas
emissions, recognizing that methane emissions from shale gas are more
depleted in <inline-formula><mml:math id="M38" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> than for conventional natural gas or other fossil fuels
as considered by Worden et al. (2017). For this analysis, we accept that net
total emissions have increased by 24.7 Tg per year (<inline-formula><mml:math id="M39" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">14.0</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year)
since 2007, driven by an increase of <inline-formula><mml:math id="M40" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">28.4</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year for
the sum of biogenic emissions and emissions from fossil fuels and a decrease
of <inline-formula><mml:math id="M41" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">3.7</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year for emissions from biomass burning
(Worden et al., 2017).</p>

      <?xmltex \floatpos{p}?><fig id="Ch1.F3" specific-use="star"><?xmltex \currentcnt{3}?><label>Figure 3</label><caption><p id="d1e660"><bold>(a)</bold> On the <inline-formula><mml:math id="M42" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axis, <inline-formula><mml:math id="M43" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values for methane from
biogenic sources, fossil fuel, and biomass burning as presented in Worden et al. (2017) for values from Schwietzke et al. (2016); width of horizontal
bars represents the 95 % confidence limits for these values. Triangle
indicates the flux-weighted mean input of methane to the atmosphere. The
<inline-formula><mml:math id="M44" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axis shows mean estimates from Worden et al. (2017) for the increase and
decrease in methane emissions from particular sources since 2007 as
calculated using the <inline-formula><mml:math id="M45" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values of Schwietzke et al. (2016). <bold>(b)</bold> On the <inline-formula><mml:math id="M46" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axis, <inline-formula><mml:math id="M47" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values as in Fig. 3a, except
the value for fossil fuels does not include shale gas and a separate
estimate for shale-gas value is included (see text). The <inline-formula><mml:math id="M48" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axis indicates
estimates developed in this paper for the increase or decrease in methane
emissions since 2008.</p></caption>
        <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019-f03.png"/>

      </fig>

      <?pagebreak page3037?><p id="d1e742">We start with Eq. (1), which expresses the findings of Worden et al. (2017):
          <disp-formula id="Ch1.E1" content-type="numbered"><label>1</label><mml:math id="M49" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">28.4</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mrow class="unit"><mml:mi mathvariant="normal">Tg</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
        where <inline-formula><mml:math id="M50" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M51" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> are the estimates from Worden et al. (2017) for the
increase respectively in biogenic emissions and fossil-fuel emissions of
methane globally since 2007. Equation (2) explicitly considers methane
emissions from shale gas:
          <disp-formula id="Ch1.E2" content-type="numbered"><label>2</label><mml:math id="M52" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">28.4</mml:mn><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mrow class="unit"><mml:mi mathvariant="normal">Tg</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">yr</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
        where <inline-formula><mml:math id="M53" display="inline"><mml:mrow><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is our new estimate for the increase in the biogenic fluxes
since 2007, FF<inline-formula><mml:math id="M54" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:math></inline-formula> is our new estimate for the increase in fossil-fuel
emissions other than shale gas since 2007, and SG is our estimate for
emissions from shale gas since 2007. Subtracting Eq. (2) from Eq. (1),
          <disp-formula id="Ch1.E3" content-type="numbered"><label>3</label><mml:math id="M55" display="block"><mml:mrow><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>-</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e912">Equation (4) builds on Eq. (3) and reweights the information in Fig. 3a for
the difference between most fossil fuels and shale gas, multiplying global
mass fluxes for each source by the difference between the <inline-formula><mml:math id="M56" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>
ratio of each source and the flux-weighted mean for all sources:
          <disp-formula id="Ch1.E4" content-type="numbered"><label>4</label><mml:math id="M57" display="block"><mml:mtable rowspacing="0.2ex" columnspacing="1em" class="split" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mfenced open="[" close="]"><mml:mrow><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mfenced open="[" close="]"><mml:mrow><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">FF</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mo>-</mml:mo><mml:mfenced close=")" open="("><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>⋅</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula>
        whereD<inline-formula><mml:math id="M58" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:math></inline-formula>,D<inline-formula><mml:math id="M59" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">FF</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:math></inline-formula>, and D<inline-formula><mml:math id="M60" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:math></inline-formula> are the differences in
the <inline-formula><mml:math id="M61" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio of biogenic emissions, fossil fuels, and shale
gas compared to the flux-weighted mean <inline-formula><mml:math id="M62" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio for all
sources (A). The <inline-formula><mml:math id="M63" display="inline"><mml:mi>x</mml:mi></mml:math></inline-formula> axis of Fig. 3b shows the <inline-formula><mml:math id="M64" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> for each
source; note that the <inline-formula><mml:math id="M65" display="inline"><mml:mi>y</mml:mi></mml:math></inline-formula> axis is the estimate of the change in emissions for
each of the sources that we derive below. Next, we multiply both sides of
Eq. (3) byD<inline-formula><mml:math id="M66" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:math></inline-formula>,
          <disp-formula id="Ch1.E5" content-type="numbered"><label>5</label><mml:math id="M67" display="block"><mml:mtable class="split" rowspacing="0.2ex" columnspacing="1em" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mfenced open="[" close="]"><mml:mrow><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">B</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced></mml:mrow></mml:mfenced><mml:mo>+</mml:mo><mml:mfenced open="[" close="]"><mml:mrow><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mo>-</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>⋅</mml:mo><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula></p>
      <p id="d1e1238">Subtracting Eq. (5) from Eq. (4),
          <disp-formula id="Ch1.E6" content-type="numbered"><label>6</label><mml:math id="M68" display="block"><mml:mtable class="split" columnspacing="1em" rowspacing="0.2ex" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mfenced open="[" close="]"><mml:mrow><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">FF</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced></mml:mrow></mml:mfenced></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mo>-</mml:mo><mml:mfenced close="]" open="["><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>⋅</mml:mo><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced></mml:mrow></mml:mfenced><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula></p>
      <p id="d1e1337">Rearranging Eq. (6) to solve for SG,
          <disp-formula id="Ch1.E7" content-type="numbered"><label>7</label><mml:math id="M69" display="block"><mml:mtable class="split" rowspacing="0.2ex" columnspacing="1em" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>=</mml:mo><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">W</mml:mi></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:mrow></mml:mfenced><mml:mo>⋅</mml:mo><mml:mfenced open="(" close=")"><mml:mrow><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">FF</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced><mml:mo>/</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mfenced close=")" open="("><mml:mrow><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">D</mml:mi><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:mrow></mml:mfenced><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula></p>
      <p id="d1e1428">Note that from Worden et al. (2017), FF<inline-formula><mml:math id="M70" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">W</mml:mi></mml:msub></mml:math></inline-formula> is 16.4 Tg per year.</p>
      <p id="d1e1440">Although our expectation is that the methane in shale gas is depleted in
<inline-formula><mml:math id="M71" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> relative to conventional natural gas, the <inline-formula><mml:math id="M72" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratios
for the methane in both conventional gas reservoirs and in shale gas vary
substantially, changing with the maturity of the gas and several other
factors (Golding et al., 2013; Hao and Zou, 2013; Tilley and Muehlenbachs,
2013). The large data set of Sherwood et al. (2017) suggests no systematic
difference between the average ratio for shale gas and the average for
conventional gas. However, some of the data listed as shale gas in that data
set are actually for methane that has migrated from shale to reservoirs
(Tilley et al., 2011) and therefore may have been partially oxidized and
fractionated (Hao and Zou, 2013). In other cases, the data appear to come
both from conventional vertical wells and shale-gas horizontal wells in the
same region, making interpretation ambiguous (Rodriguez and Philp, 2010;
Zumberge et al., 2012). Note that in the Barnett shale region, Texas, the
<inline-formula><mml:math id="M73" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio for methane emitted to the atmosphere (<inline-formula><mml:math id="M74" display="inline"><mml:mo lspace="0mm">-</mml:mo></mml:math></inline-formula>46.5 ‰; Townsend-Small et al., 2015) is more depleted than the
average for wells reported in the Sherwood et al. (2017) data set: <inline-formula><mml:math id="M75" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>44.8 ‰ for “group 2A and 2B” wells and <inline-formula><mml:math id="M76" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>38.5 ‰ for
“group 1” wells (Rodriguez and Philp, 2010) and a <inline-formula><mml:math id="M77" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>41.1 ‰ average value
(Zumberge et al., 2012). For our analysis, we use the mean of the <inline-formula><mml:math id="M78" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio (<inline-formula><mml:math id="M79" display="inline"><mml:mo lspace="0mm">-</mml:mo></mml:math></inline-formula>46.9 ‰) from three studies where the
methane clearly came from horizontal, high-volume fractured shale wells: <inline-formula><mml:math id="M80" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>47.0 ‰ for Bakken shale, North Dakota (Schoell et al., 2011),
<inline-formula><mml:math id="M81" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>46.5 ‰ for Barnett shale, Texas (Townsend-Small et al., 2015),
and <inline-formula><mml:math id="M82" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>47.3 ‰ for Utica shale, Ohio (Botner et al., 2018). Note
that several studies have reported mean <inline-formula><mml:math id="M83" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratios for methane
from organic-rich shales that are more depleted in <inline-formula><mml:math id="M84" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> (more negative)
than this: <inline-formula><mml:math id="M85" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>50.7 (Martini et al., 1998) for Antrim shale, Michigan, <inline-formula><mml:math id="M86" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>53.3
(McIntosh et al., 2002) and <inline-formula><mml:math id="M87" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>51.1 (Schlegel et al., 2011) for New Albany
shale, Illinois, and <inline-formula><mml:math id="M88" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>49.3 (Osborn and McIntosh, 2010) for a Devonian shale
in Ohio. However, these shales are not typical of the major shale plays
supporting the huge increase in gas production over the past decade.</p>
      <p id="d1e1606">The average <inline-formula><mml:math id="M89" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio for methane in the atmosphere (A) in
2005 was <inline-formula><mml:math id="M90" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>47.2 ‰ (Schaefer et al., 2016), which reflects a
flux-weighted mean input of methane with a <inline-formula><mml:math id="M91" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio of <inline-formula><mml:math id="M92" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>53.5 ‰. This flux-weighted mean value is approximately 6.3 ‰ more depleted in <inline-formula><mml:math id="M93" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> because of fractionation during the
oxidation of methane in the atmosphere (Schwietzke et al., 2016; Sherwood et al., 2017). In our analysis, we use this flux-weighted mean value of <inline-formula><mml:math id="M94" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>53.5 ‰. Therefore, the mean value for D<inline-formula><mml:math id="M95" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">FF</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:math></inline-formula> is <inline-formula><mml:math id="M96" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>9.5 ‰, the value for D<inline-formula><mml:math id="M97" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">B</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:math></inline-formula> is 9.0 ‰, and the value for D<inline-formula><mml:math id="M98" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>-</mml:mo><mml:mi mathvariant="normal">A</mml:mi></mml:mrow></mml:msub></mml:math></inline-formula> is <inline-formula><mml:math id="M99" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>6.6 ‰ (Fig. 3b). Substituting these values into Eq. (7), we
see that
          <disp-formula id="Ch1.E8" content-type="numbered"><label>8</label><mml:math id="M100" display="block"><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1.19</mml:mn><mml:mo>⋅</mml:mo><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub><mml:mo>+</mml:mo><mml:mn mathvariant="normal">19.4</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
</sec>
<sec id="Ch1.S5">
  <label>5</label><title>Estimating increased methane fluxes for coal, oil, and natural gas</title>
      <p id="d1e1761">Next, we estimate the likely contributions from coal and oil to the
increased methane emissions over the past decade. We estimate the increase
in methane emissions from coal between 2006 and 2016 to be 1.3 Tg per year,
based on the rise in global coal production of 27 %, with almost all of
this due to surface-mined coal in China (IEA, 2008, 2017) and using a
well-accepted emission factor of 870 g methane per ton of surface-mined coal
(Howarth et al., 2011). Methane emissions from surface-mined coal tend to be
low, as much of the<?pagebreak page3038?> methane that was once associated with the coal has
degassed over geological time. This estimate is very close to the 1.1 Tg per year increase from coal emissions in China between 2009 and 2015 as
estimated based on satellite observations (Miller et al., 2019). For oil,
global production increased by 9.6 % (IEA, 2008, 2017), thereby increasing
methane emissions by approximately 1.6 Tg per year (using emission factors
from NETL 2008; as detailed in Howarth et al., 2011). Therefore, of the
increase in 28.4 Tg per year from fossil fuels plus biogenic sources since
2005 (see discussion above), we estimate 2.9 Tg per year to be from increased
emissions from coal and oil, leaving an increase of approximately 25.5 Tg per year from natural gas (including shale gas) plus biogenic sources.</p>
      <p id="d1e1764">As noted above, shale gas accounted for 63 % of the global increase in all
natural gas production between 2005 and 2015 (EIA, 2016; IEA, 2017). If we
make the simplifying assumption that for both shale gas and conventional
natural gas, emissions are equal as a percentage of the gas produced, then
          <disp-formula id="Ch1.E9" content-type="numbered"><label>9</label><mml:math id="M101" display="block"><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.63</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
        and
          <disp-formula id="Ch1.E10" content-type="numbered"><label>10</label><mml:math id="M102" display="block"><mml:mrow><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.37</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
        where TG is total increase in emissions from all natural gas. Note that we
test this assumption later in our sensitivity analyses, since some research
indicates that emissions from shale gas are higher than for conventional gas as a
percentage of gas production. Rearranging Eq. (9) for TG and substituting
into Eq. (10),
          <disp-formula id="Ch1.E11" content-type="numbered"><label>11</label><mml:math id="M103" display="block"><mml:mrow><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.37</mml:mn><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>/</mml:mo><mml:mn mathvariant="normal">0.63</mml:mn><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mspace width="1em" linebreak="nobreak"/><mml:mi mathvariant="normal">or</mml:mi><mml:mspace linebreak="nobreak" width="1em"/><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.59</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
        FF<inline-formula><mml:math id="M104" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:math></inline-formula> is the sum of CG (<inline-formula><mml:math id="M105" display="inline"><mml:mrow><mml:mn mathvariant="normal">0.59</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">SG</mml:mi></mml:mrow></mml:math></inline-formula>) plus the emissions from oil and coal
(2.9 Tg per year), or
          <disp-formula id="Ch1.E12" content-type="numbered"><label>12</label><mml:math id="M106" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">0.59</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>)</mml:mo><mml:mo>+</mml:mo><mml:mn mathvariant="normal">2.9</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e1896">Substituting Eq. (12) into Eq. (8) and solving for SG, we estimate that the
increase in shale-gas emissions between 2005 and 2015 was 9.4 Tg per year
(Table 1; Fig. 3b). From Eq. (11), increased emissions from conventional
natural gas are then estimated to be 5.5 Tg per year, emissions from all natural gas
(shale plus conventional) are estimated to be 14.9 Tg per year, and emissions from all fossil fuels
(including coal and oil) are estimated to be 17.8 Tg per year. From Eq. (3), increased
emissions from biogenic sources are estimated to be 10.6 Tg per year. While the
biogenic sources are important, the increase in fossil-fuel emissions has
been greater, and shale gas makes up more than half of these increased
fossil-fuel emissions.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><?xmltex \currentcnt{1}?><label>Table 1</label><caption><p id="d1e1903">Estimates for sources of increased or decreased methane emissions
to the atmosphere in recent years (teragrams per year). All values are positive,
except as specified.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="left"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">This study<inline-formula><mml:math id="M110" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">Worden et al.<inline-formula><mml:math id="M111" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">b</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4">Schwietzke et al.<inline-formula><mml:math id="M112" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">c</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">(2017)</oasis:entry>
         <oasis:entry colname="col4">(2016)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">All fossil fuels</oasis:entry>
         <oasis:entry colname="col2">17.8</oasis:entry>
         <oasis:entry colname="col3">16.4</oasis:entry>
         <oasis:entry colname="col4">Negative <inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">18</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">(<inline-formula><mml:math id="M114" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">3.6</mml:mn></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{3mm}}?>– Shale gas</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{6mm}}?>9.4</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{3mm}}?>– Conventional gas</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{6mm}}?>5.5</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{3mm}}?>– Oil</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{6mm}}?>1.6</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{3mm}}?>– Coal</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{6mm}}?>1.3</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Biogenic sources</oasis:entry>
         <oasis:entry colname="col2">10.6</oasis:entry>
         <oasis:entry colname="col3">12.0</oasis:entry>
         <oasis:entry colname="col4"><inline-formula><mml:math id="M115" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">27</mml:mn></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">(<inline-formula><mml:math id="M116" display="inline"><mml:mrow><mml:mo>±</mml:mo><mml:mn mathvariant="normal">2.5</mml:mn></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col4"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e1906"><inline-formula><mml:math id="M107" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula> Time period is 2008–2014 compared to 2000–2007.
<inline-formula><mml:math id="M108" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">b</mml:mi></mml:msup></mml:math></inline-formula> Time period is 2008–2014 compared to 2000–2007, using the Schwietzke et al. (2016) data set with values from
their Fig. 4 and assuming a
decrease in biomass burning of 3.7 Tg per year. Uncertainty is as shown in
original publication.
<inline-formula><mml:math id="M109" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">c</mml:mi></mml:msup></mml:math></inline-formula> Time period is for 2003–2013 compared to 1985–2002, with values from
their Fig. 2b. Uncertainties are large, and only mean differences shown
here.</p></table-wrap-foot></table-wrap>

</sec>
<sec id="Ch1.S6">
  <label>6</label><title>Comparison with prior estimates</title>
      <p id="d1e2166">Our best estimate for the increase in methane emissions from all fossil
fuels since 2008 (shale gas, conventional natural gas, coal, and oil) of
17.8 Tg per year is 9 % larger than the mean estimate of Worden et al. (2017) of 16.4 Tg per year (Table 1). Our estimate for the increased
emissions from biogenic sources, 10.6 Tg per year, is 12 % lower than the
Worden et al. (2017) estimate of 12 Tg per year (Table 1). Thus, our
estimates are not greatly different from those of Worden et al. (2017),
although our estimate for fossil fuels is larger and our estimate for
biogenic fluxes lower than their estimates. On the other hand, comparing
emissions for the 2003–2013 period with those from the late 20th
century, Schwietzke et al. (2016) concluded that biogenic emissions had
risen by <inline-formula><mml:math id="M117" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">27</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year, while fossil-fuel emissions had
decreased by <inline-formula><mml:math id="M118" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">18</mml:mn></mml:mrow></mml:math></inline-formula> Tg per year. And Schaefer et al. (2016)
concluded that increased methane emissions since 2006 have been “predominantly
biogenic” and that fossil-fuel emissions likely have fallen.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><?xmltex \currentcnt{2}?><label>Table 2</label><caption><p id="d1e2192">Exploration of sensitivity to assumptions for estimates of increase
in global methane emissions in recent years (teragrams per year).</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="left"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Base analysis<inline-formula><mml:math id="M124" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">Increased emission factor</oasis:entry>
         <oasis:entry colname="col4">Explicit consideration</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">for shale gas</oasis:entry>
         <oasis:entry colname="col4">of shale oil</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">(sensitivity test no. 1)<inline-formula><mml:math id="M125" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">b</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4">(sensitivity test no. 2)<inline-formula><mml:math id="M126" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">c</mml:mi></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">All fossil fuels</oasis:entry>
         <oasis:entry colname="col2">17.8</oasis:entry>
         <oasis:entry colname="col3">18.0</oasis:entry>
         <oasis:entry colname="col4">18.2</oasis:entry>
       <?xmltex \interline{[8.535827pt]}?></oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{6mm}}?>– All natural gas</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{6mm}}?>14.9</oasis:entry>
         <oasis:entry colname="col3"><?xmltex \hack{\hspace{6mm}}?>15.1</oasis:entry>
         <oasis:entry colname="col4"><?xmltex \hack{\hspace{6mm}}?>12.0</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{11mm}}?>– Shale gas</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{11mm}}?>9.4</oasis:entry>
         <oasis:entry colname="col3"><?xmltex \hack{\hspace{11mm}}?>10.8</oasis:entry>
         <oasis:entry colname="col4"><?xmltex \hack{\hspace{11mm}}?>7.8</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{11mm}}?>– Conventional gas</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{11mm}}?>5.5</oasis:entry>
         <oasis:entry colname="col3"><?xmltex \hack{\hspace{11mm}}?>4.3</oasis:entry>
         <oasis:entry colname="col4"><?xmltex \hack{\hspace{11mm}}?>4.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{6mm}}?>– All oil</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{6mm}}?>1.6</oasis:entry>
         <oasis:entry colname="col3"><?xmltex \hack{\hspace{6mm}}?>1.6</oasis:entry>
         <oasis:entry colname="col4"><?xmltex \hack{\hspace{6mm}}?>4.9</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{11mm}}?>– Shale oil</oasis:entry>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"><?xmltex \hack{\hspace{11mm}}?>4.2</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{11mm}}?>– Conventional oil</oasis:entry>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"><?xmltex \hack{\hspace{11mm}}?>0.7</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"><?xmltex \hack{\hspace{6mm}}?>– Coal</oasis:entry>
         <oasis:entry colname="col2"><?xmltex \hack{\hspace{6mm}}?>1.3</oasis:entry>
         <oasis:entry colname="col3"><?xmltex \hack{\hspace{6mm}}?>1.3</oasis:entry>
         <oasis:entry colname="col4"><?xmltex \hack{\hspace{6mm}}?>1.3</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Biogenic sources</oasis:entry>
         <oasis:entry colname="col2">10.6</oasis:entry>
         <oasis:entry colname="col3">10.4</oasis:entry>
         <oasis:entry colname="col4">10.2</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e2195"><inline-formula><mml:math id="M119" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">a</mml:mi></mml:msup></mml:math></inline-formula> Base analysis is from equations Eq. (1) to Eq. (12) and is
also presented in Table 1. Assumptions include equivalent percentage
emissions as a function of production for shale gas and conventional natural
gas and no contribution of <inline-formula><mml:math id="M120" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>-depleted methane from tight shale-oil
production.
<inline-formula><mml:math id="M121" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">b</mml:mi></mml:msup></mml:math></inline-formula> Same assumptions as for the base analysis, except shale-gas emissions
are assumed to be 50 % greater than those from conventional natural gas,
expressed as a percentage of production.
<inline-formula><mml:math id="M122" display="inline"><mml:msup><mml:mi/><mml:mi mathvariant="normal">c</mml:mi></mml:msup></mml:math></inline-formula> Same assumptions as for the base analysis, except emission of
<inline-formula><mml:math id="M123" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>-depleted methane from shale oil is explicitly considered.</p></table-wrap-foot></table-wrap>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4" specific-use="star"><?xmltex \currentcnt{4}?><label>Figure 4</label><caption><p id="d1e2490"><bold>(a)</bold> Gas blowdown for maintenance on a pipeline in Yates
County, New York. While methane is invisible, the cooling caused by the blowdown
condenses water vapor, leading to the obvious cloud. Photo courtesy of Jack
Ossont. <bold>(b, c)</bold> Gas storage tanks receiving natural gas from feeder pipelines
before compression for transport in high-pressure pipelines at the Haynseville
shale formation, Texas. Photo on left was taken with a normal camera. Photo
on the right was taken with a forward-looking infrared (FLIR) camera tuned to the infrared spectrum of
methane, allowing visualization of methane, which is invisible in the normal
camera view and to the naked eye. Photo courtesy of Sharon Wilson.</p></caption>
        <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://bg.copernicus.org/articles/16/3033/2019/bg-16-3033-2019-f04.png"/>

      </fig>

      <p id="d1e2505">We estimate that shale gas has contributed 33 % of the global increase in all
methane emissions in recent years (Table 1). Since virtually all shale-gas
development globally through 2015 occurred in North America (mostly in the
United States but also western Canada), we conclude that at least 33 % of
the increase in methane fluxes came from North America. This is consistent
with the work of Turner et al. (2016), who used satellite data to conclude
that 30 % to 60 % of the global increase in methane emissions between
2002 and 2014 came from the United States. On the other hand, Nisbet et al. (2016, 2019) used monitoring data to infer spatial changes in methane
emissions over time and emphasized that much of the increase in recent years
originated in the tropics and Southern Hemisphere, although they noted that
the northern temperate latitude played a major role in the large increase in
emissions in 2014 (Nisbet et al., 2019), a time of major increase in shale-gas development (EIA, 2016). While our estimate for increased emissions from
fossil fuels is only marginally greater than that of the Worden et al. (2017) paper upon which we build our analysis, we demonstrate the importance
of shale gas as a major part of these increased fossil-fuel emissions and
thereby explicitly link the increased emissions to North America.</p>
      <p id="d1e2508">Our estimate of increased emissions of 9.4 Tg per year from shale-gas
development is quite reasonable in light of the growing body of evidence
from measurements made at local to regional scales. Between 2005 and 2015,
global shale-gas production rose by 404 billion cubic meters per year (Fig. 2b; EIA, 2016). Assuming that 93 % of natural gas is composed of methane
(Schneising et al., 2014), our estimate of the increase in methane emissions
from shale gas represents 3.5 % of the shale-gas production (270 Tg per year of methane produced from shale-gas operations on average in 2015). This
estimate of 3.5 % (based on global change in the <inline-formula><mml:math id="M127" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> content of
methane) represents full life-cycle emissions, including those from the gas
well site, transportation, processing, storage systems, and final
distribution to customers. Our estimate is well within the range reported in
several recent studies for shale gas and in fact is at the low end for many
(but<?pagebreak page3039?> not all) of these studies (Howarth et al., 2011; Pétron et al., 2014;
Karion et al., 2013; Caulton et al., 2014; Schneising et al., 2014; Howarth,
2014). Alvarez et al. (2018) recently presented a summary estimate for
natural gas emissions in the United States (both conventional and shale gas)
of 2.3 % using bottom-up, facility-based data. However, they noted that
top-down estimates from approaches such as airplane flyovers give higher
values than the bottom-up estimates they emphasized. In fact, a careful
comparison of bottom-up and top-down approaches for one shale-gas field
showed 45 % higher emissions from the top-down approach due to under-sampling of some emission events by the bottom-up, facility-based approach
(Vaughn et al., 2018). Further, Alvarez et al. (2018) used a very low value
for the methane emissions from local distribution pipelines, only 0.08 %
(see discussion in Howarth et al., 2011). Many studies suggest that distribution
emissions in Boston, Los Angeles, Indianapolis, and Texas cities may be as
high as 2.5 % or more, not 0.08 % (Howarth et al., 2011; McKain et al., 2015; Lamb et al., 2016; Wunch et al., 2016), so a full life cycle of
3.5 % emissions from shale gas over the past decade is quite plausible
and perhaps even low.</p>
</sec>
<sec id="Ch1.S7">
  <label>7</label><title>Sensitivity analyses</title>
      <p id="d1e2531">Our analysis contains two major assumptions: (1) that methane emissions as a
percentage of gas produced are the same for shale gas and conventional
natural gas (Eqs. 9 and  10); and (2) that emissions from oil have
remained proportional to the global rate of oil production. Here we<?pagebreak page3040?> explore
the sensitivity of our analysis to these assumptions. With regard to the
first assumption, some evidence suggests that percent emissions may be
higher from shale gas than from conventional natural gas, perhaps due to
venting at the time of flowback following high-volume hydraulic fracturing
of shale-gas wells (Howarth et al., 2011) and also due to release of methane
from trapped pockets when drilling down through a very long legacy (often a
century or more) of prior fossil-fuel operations (coal, oil, and gas) to
reach the deeper shale formations (Caulton et al., 2014; Howarth, 2014). For
this first sensitivity analysis, we modify equations Eq. (9) through Eq. (12) with new equations Eq. (A1) through Eq. (A4) to reflect a 50 % higher
emission factor for shale gas than for conventional gas, as proposed in
Howarth et al. (2011; see Appendix A). With this change in assumptions,
estimated shale-gas emissions increase by 12 % (10.8 instead of 9.4 Tg per year), which corresponds to a life-cycle emission factor of 4.0 % rather
than 3.5 %. Biogenic emissions remain virtually unchanged (10.4 instead of
10.6 Tg per year), as do total fossil-fuel emissions (18 instead of 17.8 Tg per year; Table 2).</p>
      <p id="d1e2534">Our second major assumption in the base analysis is that methane emission
factors for oil production have remained constant over time as a function of
production. This may not be true, since 60 % of the increase in global oil
production between 2005 and 2015 was due to tight oil production from shales
using the same technologies that allowed shale-gas development,
high-precision directional drilling<?pagebreak page3041?> and high-volume hydraulic fracturing
(calculated from data in EIA, 2015,  2018). Large quantities of methane
are often co-produced with this tight shale oil, and because oil is a much
more valuable product than natural gas, for shale-oil fields removed from
easy access to natural gas markets, much of the methane may be vented or
flared rather than delivered to the market. This may be part of the reason for
the large increase in methane emissions between 2008 and 2011 in the Bakken
shale fields of North Dakota (Schneising et al., 2014).</p>
      <p id="d1e2537">For sensitivity scenario no. 2, we modify Eq. (9) through Eq. (12) with new Eq. (B1) through Eq. (B4) to allow for higher
emissions associated with shale oil than from conventional oil production (see Appendix B). For this, we follow the approach of Schneising et al. (2014)
in combining shale gas and shale oil, scaling the increase in production
since 2005 by the energy value of the two products. As in our baseline
analysis developed in equations Eq. (1) through Eq. (12), we assume that
conventional natural gas and shale gas have the same percentage methane
emission per unit of produced gas. Here we further assume that shale oil has
the same emission rate as well, scaled to the energy content of oil compared
to natural gas. This sensitivity analysis again has very little influence on
either total emissions from fossil fuels (18.2 instead of 17.8 Tg per year)
or biogenic emissions (10.2 instead of 10.6 Tg per year; Table 2). The
contribution from shale gas falls somewhat (from 9.4 to 7.8 Tg per year), as
does that from conventional natural gas (from 5.5 to 4.2 Tg per year), while
shale oil becomes an important emission source (4.2 Tg per year). Overall in
this scenario, increased emissions from fossil fuels extracted from shales
(gas plus oil) are 12 Tg per year, two-thirds of the total increase due to
fossil fuels.</p>
</sec>
<sec id="Ch1.S8" sec-type="conclusions">
  <label>8</label><title>Conclusions</title>
      <p id="d1e2548">We conclude that increased methane emissions from fossil fuels likely exceed
those from biogenic sources over the past decade (since 2007). The increase
in emissions from shale gas (perhaps in combination with those from shale
oil) makes up more than half of the total increased fossil-fuel emissions.
That is, the commercialization of shale gas and oil in the 21st century
has dramatically increased global methane emissions.</p>
      <p id="d1e2551">Note that while methane emissions are often referred to as “leaks”, some
of the emissions include purposeful venting, including the release of gas
during the flowback period immediately following hydraulic fracturing, the
rapid release of gas from blowdowns during emergencies but also for routine
maintenance on pipelines and compressor stations (Fig. 4a), and the
steadier but more subtle release of gas from storage tanks (Fig. 4b) and
compressor stations to safely maintain pressures (Howarth et al., 2011). This
suggests large opportunities for reducing emissions, but at what cost? Do
large capital investments for rebuilding natural gas infrastructure make
economic sense, or would it be better to move towards phasing natural gas out as an
energy source and instead invest in a 21st-century energy
infrastructure that embraces renewable energy and much more efficient heat
and transportation through electrification (Jacobson et al., 2013)?</p>
      <p id="d1e2554">In October 2018, the Intergovernmental Panel on Climate Change issued a
special report, responding to the call of the United Nations COP21
negotiations to keep the planet well below 2 <inline-formula><mml:math id="M128" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C of the pre-industrial
baseline (IPCC, 2018). They noted the need to reduce both carbon dioxide and
methane emissions, and they recognized that the climate system responds more
quickly to methane: reducing methane emissions offers one of the best routes
for immediately slowing the rate of global warming (Shindell et al., 2012). Given
our finding that natural gas (both shale gas and conventional gas) is
responsible for much of the recent increases in methane emissions, we
suggest that the best strategy is to move as quickly as possible away from
natural gas, reducing both carbon dioxide and methane emissions. Natural gas
is not a bridge fuel (Howarth, 2014).</p>
      <p id="d1e2566">Finally, in addition to contributing to climate change, methane emissions
lead to increased ground-level ozone levels, with significant damage to
public health and agriculture. Based on the social cost of methane emissions
of USD 2700 to USD 6000 per ton (Shindell, 2015), our baseline estimate for
increased emissions from shale gas of 9.4 Tg per year corresponds to damage
to public health, agriculture, and the climate of USD 25 billion to USD 55 billion
per year for each of the past several years. This is comparable to the
wholesale value for this shale gas over these years.</p>
</sec>

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

      <p id="d1e2573">No data sets were used in this article.</p>
  </notes><?xmltex \hack{\clearpage}?><app-group>

<?pagebreak page3042?><app id="App1.Ch1.S1">
  <?xmltex \currentcnt{A}?><label>Appendix A</label><?xmltex \opttitle{Sensitivity case no.~1: emissions per unit of gas produced
assumed to be 50\,{\%} greater for shale gas than for conventional gas}?><title>Sensitivity case no. 1: emissions per unit of gas produced
assumed to be 50 % greater for shale gas than for conventional gas</title>
      <p id="d1e2588">First we modify Eqs. (9) and  (10) as follows to reflect that methane
emissions per unit of gas produced are 50 % greater for shale gas than for
conventional natural gas:
          <disp-formula id="App1.Ch1.S1.E13" content-type="numbered"><label>A1</label><mml:math id="M129" display="block"><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1.2</mml:mn><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">0.63</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mspace linebreak="nobreak" width="1em"/><mml:mtext>or</mml:mtext><mml:mspace linebreak="nobreak" width="1em"/><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.76</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
        and
          <disp-formula id="App1.Ch1.S1.E14" content-type="numbered"><label>A2</label><mml:math id="M130" display="block"><mml:mrow><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.8</mml:mn><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:mn mathvariant="normal">0.37</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mspace width="1em" linebreak="nobreak"/><mml:mtext>or</mml:mtext><mml:mspace width="1em" linebreak="nobreak"/><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.30</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e2676">Rearranging Eq. (A1) for TG and substituting into Eq. (A2),
          <disp-formula id="App1.Ch1.S1.E15" content-type="numbered"><label>A3</label><mml:math id="M131" display="block"><mml:mrow><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.30</mml:mn><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>/</mml:mo><mml:mn mathvariant="normal">0.76</mml:mn><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mspace width="1em" linebreak="nobreak"/><mml:mtext>or</mml:mtext><mml:mspace width="1em" linebreak="nobreak"/><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.40</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e2721">Since FF<inline-formula><mml:math id="M132" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:math></inline-formula> is the sum of CG and the 2.9 Tg per year emissions for oil
and coal,
          <disp-formula id="App1.Ch1.S1.E16" content-type="numbered"><label>A4</label><mml:math id="M133" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.40</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">2.9</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e2758">Substituting Eq. (A4) into Eq. (8) and solving for SG, we estimate that the
increase in shale-gas emissions between 2005 and 2015 was 10.8 Tg per year
(Table 2). From Eq. (A3), for conventional natural gas, CG <inline-formula><mml:math id="M134" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 4.3 Tg per year. The increase in total fossil-fuel emissions are estimated to be the
contributions from coal (1.3 Tg per year) and oil (1.6 Tg per year) plus SG
and CG, or 18 Tg per year. From Eq. (3), biogenic emissions are estimated to
have increased by 10.4 Tg per year. These values are reported in Table 2.</p>
</app>

<app id="App1.Ch1.S2">
  <?xmltex \currentcnt{B}?><label>Appendix B</label><title>Sensitivity case no. 2: explicit consideration of shale oil
(tight oil)</title>
      <p id="d1e2776">For the base analysis presented in the main text using equations Eq. (1)
through Eq. (12), we assumed that increased emissions from the additional
oil development over the past decade were proportional to the increase in
that rate of development. That is, the oil produced in recent years had the
same emission factor as that for oil produced a decade or more ago. However,
60 % of the increase in oil production globally between 2005 and 2015 was
for tight oil from shale formations (calculated from data in EIA, 2015, 2018), and methane emissions from this shale oil may be greater than for
conventional oil. In sensitivity case no. 2, we consider increased
emissions from conventional oil and from tight shale oil separately. For
conventional oil, the increase in emissions is 40 % of the total oil
emissions from the base analysis (40 % of 1.6 Tg per year, or 0.65 Tg per year, rounded to 0.7 in Table 2), reflecting that conventional oil
contributed 40 % to the growth in oil production between 2005 and 2015.</p>
      <p id="d1e2779">For the tight shale oil, we follow the approach used by Schneising et al. (2014): the increases in methane emissions from shale gas and shale oil are
considered together, normalized to the energy content of the two fuels.
Shale-gas production increased by 405 billion cubic meters per year between 2005
and 2015 (EIA, 2016). With an energy content of 37 MJ per cubic meter, this
reflects an increase in 15.9 trillion MJ per year. For shale oil, production
increased by 230 liters per year between 2005 and 2015 (EIA, 2015, 2018).
With an energy content of 38 MJ per liter, this reflects an increase in 8.9 trillion MJ per year. Conventional natural gas production increased by 238 billion cubic meters per year between 2005 and 2015 (EIA, 2016). With an energy
content of 37 MJ m<inline-formula><mml:math id="M135" 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>, this reflects an increase in 8.8 trillion MJ
per year. Therefore, the sum of the increase in production for shale gas,
shale oil, and conventional natural gas is 33.6 trillion megajoules per year. Shale
gas represents 48 % of this, shale oil represents 26 %, and conventional natural
gas represents 26 %. The sum of shale gas and shale oil represents 74 %
of the total.</p>
      <p id="d1e2794">For this sensitivity analysis, we further assume that shale gas and
conventional natural gas have the same percentage emissions, as in our base
case analysis in the main text, and that the <inline-formula><mml:math id="M136" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> content of methane
from shale oil is the same as for shale gas. Using these assumptions, we
modify Eqs. (9) and  (10) as follows:
          <disp-formula id="App1.Ch1.S2.E17" content-type="numbered"><label>B1</label><mml:math id="M137" display="block"><mml:mrow><mml:mi mathvariant="normal">SG</mml:mi><mml:mi mathvariant="italic">&amp;</mml:mi><mml:mi mathvariant="normal">O</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.74</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mi mathvariant="italic">&amp;</mml:mi><mml:mi mathvariant="normal">SO</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
        and
          <disp-formula id="App1.Ch1.S2.E18" content-type="numbered"><label>B2</label><mml:math id="M138" display="block"><mml:mrow><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.26</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">TG</mml:mi><mml:mi mathvariant="italic">&amp;</mml:mi><mml:mi mathvariant="normal">SO</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
        where SG&amp;O is shale gas plus shale oil and TG&amp;SO is total natural gas
plus shale oil. Rearranging Eq. (B1) for TG&amp;SO and substituting into Eq. (B2),
          <disp-formula id="App1.Ch1.S2.E19" content-type="numbered"><label>B3</label><mml:math id="M139" display="block"><mml:mrow><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.26</mml:mn><mml:mo>⋅</mml:mo><mml:mo>(</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mi mathvariant="italic">&amp;</mml:mi><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mn mathvariant="normal">0.74</mml:mn><mml:mo>)</mml:mo><mml:mo>,</mml:mo><mml:mspace linebreak="nobreak" width="1em"/><mml:mi mathvariant="normal">or</mml:mi><mml:mspace linebreak="nobreak" width="1em"/><mml:mi mathvariant="normal">CG</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.35</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mi mathvariant="italic">&amp;</mml:mi><mml:mi mathvariant="normal">O</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e2908">Since FF<inline-formula><mml:math id="M140" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">N</mml:mi></mml:msub></mml:math></inline-formula> is the sum of CG and the 2.0 Tg per year emissions for coal
and conventional oil,
          <disp-formula id="App1.Ch1.S2.E20" content-type="numbered"><label>B4</label><mml:math id="M141" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">FF</mml:mi><mml:mi mathvariant="normal">N</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.35</mml:mn><mml:mo>⋅</mml:mo><mml:mi mathvariant="normal">SG</mml:mi><mml:mo>+</mml:mo><mml:mn mathvariant="normal">2.0</mml:mn><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p id="d1e2945">Substituting Eq. (B4) into Eq. (8) and solving for SG, we estimate that the
increase in methane emissions from shale oil plus shale gas between 2005 and
2015 was 12 Tg per year. From Eq. (B3), increased emissions from
conventional natural gas are 4.2 Tg per year (Table 2).</p>
      <?pagebreak page3043?><p id="d1e2948">The total increase in fossil-fuel emissions is estimated to be the
contributions from coal (1.3 Tg per year), conventional oil (0.7 Tg per year), and conventional natural gas (4.2 Tg per year) plus the sum for shale
gas plus shale oil (12 Tg per year), or 18.2 Tg per year. We can separately
estimate shale gas and shale oil, estimating the proportion of the sum of
the two made up by shale gas as follows:
          <disp-formula id="App1.Ch1.S2.E21" content-type="numbered"><label>B5</label><mml:math id="M142" display="block"><mml:mtable rowspacing="0.2ex" columnspacing="1em" class="split" displaystyle="true" columnalign="right left"><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mn mathvariant="normal">15.9</mml:mn><mml:mspace width="0.25em" linebreak="nobreak"/><mml:msup><mml:mtext>trillion MJ yr</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>/</mml:mo></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mo>(</mml:mo><mml:mn mathvariant="normal">15.9</mml:mn><mml:mspace width="0.25em" linebreak="nobreak"/><mml:msup><mml:mtext>trillion MJ yr</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:mtd></mml:mtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace width="0.25em" linebreak="nobreak"/><mml:mspace linebreak="nobreak" width="0.25em"/><mml:mo>+</mml:mo><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mtext>8.9 MJ yr</mml:mtext><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.64</mml:mn></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula></p>
      <p id="d1e3017">Therefore, of the increased emissions of 12 Tg per year for SG&amp;O, the
increase for shale-gas emissions is 7.8 Tg per year and that for shale-oil
emissions is 4.2 Tg per year. These values are reported in Table 2.</p><?xmltex \hack{\clearpage}?>
</app>
  </app-group><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e3026">The authors declare that they have no conflict of interest.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e3032">We thank Tony Ingraffea, Amy Townsend-Small, Alexander Turner, Euan Nisbet, Martin Manning, Dennis Swaney, Roxanne Marino, three anonymous
reviewers, and associate editor Jack Middelburg for comments on earlier
versions of this paper. We particularly thank Dennis Swaney for help
with the analyses we report. We thank Gretchen Halpert for the artwork in
Figs. 1 and 2, Sharon Wilson for the photographs in Fig. 4b, c, and Jack
Ossont for the photograph in Fig. 4a. Tony Ingraffea helped interpret
these photographs.</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e3037">This research has been supported by the Park Foundation (grant no. 16-612) and an endowment given by David R. Atkinons to support the professorship at Cornell University held by Robert W. Howarth.</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e3043">This paper was edited by Jack Middelburg and reviewed by three anonymous referees.</p>
  </notes><ref-list>
    <title>References</title>

      <ref id="bib1.bib1"><label>1</label><?label 1?><mixed-citation>Alvarez, R. A., Zavalao-Araiza, D., Lyon, D. R., Allen, D. T., Barkley, Z. R.,
Brandt, A. R., Davis, K. J., Herndon, S. C., Jacob, D. J., Karion, A., Korts,
E. A., Lamb, B. K., Lauvaux, T., Maasakkers, J. D., Marchese, A. J., Omara, M.,
Pacala, J. W., Peiachl, J., Robinson, A. J., Shepson, P. B., Sweeney, C.,
Townsend-Small, A., Wofsy, S. C., and Hamburg, S. P.: Assessment of methane
emissions from the U.S. oil and gas supply chain, Science,  361, 186–188,
<ext-link xlink:href="https://doi.org/10.1126/science.aar7204" ext-link-type="DOI">10.1126/science.aar7204</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib2"><label>2</label><?label 1?><mixed-citation>Baldassare, F. J., McCaffrey, M. A., and Harper, J. A.: A geochemical context
for stray gas investigations in the northern Appalachian Basin: Implications
of analyses of natural gases from Neogene-through Devonian-age strata, AAPG
Bull., 98, 341–372, <ext-link xlink:href="https://doi.org/10.1306/06111312178" ext-link-type="DOI">10.1306/06111312178</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib3"><label>3</label><?label 1?><mixed-citation>Botner, E. C., Townsend-Small, A., Nash, D. B.,  Xu, X., Schimmelmann, A., and
Miller, J. H.: Monitoring concentration and isotopic composition of methane
in groundwater in the Utica Shale hydraulic fracturing region of Ohio,
Environ. Monit. Assess., 190, 322–337, <ext-link xlink:href="https://doi.org/10.1007/s10661-018-6696-1" ext-link-type="DOI">10.1007/s10661-018-6696-1</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib4"><label>4</label><?label 1?><mixed-citation>Burruss, R. C. and Laughrey, C. D.: Carbon and hydrogen isotopic reversals in
deep basin gas: evidence for limits to the stability of hydrocarbons,
Org. Geochem., 41, 1285–1296, <ext-link xlink:href="https://doi.org/10.1016/j.orggeochem.2010.09.008" ext-link-type="DOI">10.1016/j.orggeochem.2010.09.008</ext-link>,
2010.</mixed-citation></ref>
      <ref id="bib1.bib5"><label>5</label><?label 1?><mixed-citation>Caulton, D. R., Shepson, P. D., Santoro, R. L., Sparks, J. P., Howarth, R. W.,
Ingraffea, A., Camaliza, M. O., Sweeney, C., Karion, A., Davis, K. J., Stirm,
B. H., Montzka, S. A., and   Miller, B.: Toward a better understanding and
quantification of methane emissions from shale gas development, P. Natl.
Acad. Sci. USA,  111, 6237–6242, <ext-link xlink:href="https://doi.org/10.1073/pnas.1316546111" ext-link-type="DOI">10.1073/pnas.1316546111</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib6"><label>6</label><?label 1?><mixed-citation>EIA: Shale gas and tight oil and commercially produced in just four
countries, Energy Information Administration, US Department of Energy,
available at: <uri>https://www.eia.gov/todayinenergy/detail.php?id=19991</uri> (last access: 14 September 2018), 2015.</mixed-citation></ref>
      <ref id="bib1.bib7"><label>7</label><?label 1?><mixed-citation>EIA: Shale gas production drives world natural gas production
growth, Energy Information Administration, US Department of Energy,
available at: <uri>https://www.eia.gov/todayinenergy/detail.php?id=27512</uri> (last access: 12 September 2018), 2016.</mixed-citation></ref>
      <ref id="bib1.bib8"><label>8</label><?label 1?><mixed-citation>
EIA: Table 1.2, World crude oil production 1960–2017, Monthly energy review,
June 2018, Energy Information Administration, US Department of Energy, 1–244,
2018.</mixed-citation></ref>
      <ref id="bib1.bib9"><label>9</label><?label 1?><mixed-citation>Golding, S. D., Boreham, C. J., and Esterle, J. S.: Stable isotope geochemistry
of coal bed and shale gas and related production waters: A review, Int. J.
Coal Geolog., 120, 24–40, <ext-link xlink:href="https://doi.org/10.1016/j.coal.2013.09.001" ext-link-type="DOI">10.1016/j.coal.2013.09.001</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib10"><label>10</label><?label 1?><mixed-citation>Hao, F. and Zou, H.: Cause of shale gas geochemical anomalies and
mechanisms for gas enrichment and depletion in high-maturity shales, Mar.
Petrol. Geol., 44, 1–12, <ext-link xlink:href="https://doi.org/10.1016/j.marpetgeo.2013.03.005" ext-link-type="DOI">10.1016/j.marpetgeo.2013.03.005</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib11"><label>11</label><?label 1?><mixed-citation>Howarth, R. W.: A bridge to nowhere: Methane emissions and the greenhouse gas
footprint of natural gas, Energy Sci. Eng., 2, 47–60, <ext-link xlink:href="https://doi.org/10.1002/ese3.35" ext-link-type="DOI">10.1002/ese3.35</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib12"><label>12</label><?label 1?><mixed-citation>Howarth, R. W., Santoro, R., and Ingraffea, A.: Methane and the greenhouse
gas footprint of natural gas from shale formations, Clim. Change Lett.,
106, 679–690, <ext-link xlink:href="https://doi.org/10.1007/s10584-011-0061-5" ext-link-type="DOI">10.1007/s10584-011-0061-5</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib13"><label>13</label><?label 1?><mixed-citation>IEA: World Energy Outlook, International Energy Agency, available at: <uri>https://webstore.iea.org/world-energy-outlook-2008</uri>
(last access: 12 September 2018), 2008.</mixed-citation></ref>
      <ref id="bib1.bib14"><label>14</label><?label 1?><mixed-citation>IEA: Key World Energy Statistics, International Energy Agency, available at: <uri>https://www.iea.org/publications/freepublications/publication/KeyWorld2017.pdf</uri> (last access: 12 September 2018), 2017.</mixed-citation></ref>
      <ref id="bib1.bib15"><label>15</label><?label 1?><mixed-citation>
IPCC: Climate Change 2013: The Physical Science Basis. Contribution of
Working Group I to the Fifth Assessment Report of the Intergovernmental
Panel on Climate Change, Intergovernmental Panel on Climate Change, chap. 8, 659–740, 2013.</mixed-citation></ref>
      <ref id="bib1.bib16"><label>16</label><?label 1?><mixed-citation>IPCC: Summary for Policymakers, in: Global warming of 1.5 <inline-formula><mml:math id="M143" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. An
IPCC Special Report on the impacts of global warming of 1.5 <inline-formula><mml:math id="M144" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C
above pre-industrial levels and related global greenhouse gas emission
pathways, in the context of strengthening the global response to the threat
of climate change, sustainable development, and efforts to eradicate
poverty, Intergovernmental Panel on Climate Change, available at: <uri>http://www.ipcc.ch/report/sr15/</uri> (last access: 29 March 2019), 2018.</mixed-citation></ref>
      <ref id="bib1.bib17"><label>17</label><?label 1?><mixed-citation>Jacobson, M. Z., Howarth, R. W., Delucchi, M. A., Scobies, S. R., Barth,
J. M., Dvorak, M. J., Klevze, M., Katkhuda, H., Miranda, B., Chowdhury, N. A.,
Jones, R., Plano, L., and  Ingraffea, A. R.: Examining the feasibility of
converting New York State's all-purpose energy infrastructure to one using
wind, water, and sunlight, Energ. Policy, 57,  585–601, <ext-link xlink:href="https://doi.org/10.1016/j.enpol.2013.02.036" ext-link-type="DOI">10.1016/j.enpol.2013.02.036</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib18"><label>18</label><?label 1?><mixed-citation>Karion, A., Sweeney, C., Pétron, G., Frost, G., Hardesty, R. M., Kofler,
J., Miller, B. R., Newberger, T., Wolter, S., Banta, R., and Brewer, A.:
Methane emissions estimate from airborne measurements over a western United
States natural gas field, Geophys. Res. Lett., 40, 4393–4397,
<ext-link xlink:href="https://doi.org/10.1002/grl.50811" ext-link-type="DOI">10.1002/grl.50811</ext-link>, 2013.</mixed-citation></ref>
      <?pagebreak page3045?><ref id="bib1.bib19"><label>19</label><?label 1?><mixed-citation>Lamb, B. K., Cambaliza, M. O. L., Davis, K. J., Edburg, S. L., Ferrara, T. W.,
Floerchinger, C., Heimburger, A. M. F., Herndon, S., Lauvaux, T., Lavoie, T.,
Lyon, D. R., Miles, N., Prasad, K. R., Richardson, S., Roscioli, J. R., Salmon,
O. E. Shepson, P. B., Stirm, B. H., and Whetstone, J.: Direct and indirect
measurements and modeling of methane emissions in Indianapolis, Indiana,
Environ. Sci. Technol., 50, 8910–8917, <ext-link xlink:href="https://doi.org/10.1021/acs.est.6b01198" ext-link-type="DOI">10.1021/acs.est.6b01198</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib20"><label>20</label><?label 1?><mixed-citation>
Martini, A. M., Walter, L. M., Budai, J. M., Ku, T. C. W., Kaiser, C. J., and
Schoell, M.: Genetic and temporal relations between formation waters and
biogenic methane: Upper Devonian Antrim Shale, Michigan Basin, USA, Geochim.
Cosmochim. Ac., 62, 1699–1720, 1998.</mixed-citation></ref>
      <ref id="bib1.bib21"><label>21</label><?label 1?><mixed-citation>McIntosh, J. C., Walter, L. M., and Martini, A. M.: Pleistocene recharge to
mid-continent basins: effects on salinity structure and microbial gas
generation, Geochim. Cosmochim. Ac., 66, 1681–1700,
<ext-link xlink:href="https://doi.org/10.1016/S0016-7037(01)00885-7" ext-link-type="DOI">10.1016/S0016-7037(01)00885-7</ext-link>, 2002.</mixed-citation></ref>
      <ref id="bib1.bib22"><label>22</label><?label 1?><mixed-citation>McKain, K., Down, A., Raciti, S. M., Budney, J., Hutyra, L. R., Floerchinger,
C., Herndon, S. C., Nehrkorn, T., Zahniser, M. S., Jackson, R. B., Phillips,
N., and Wofsy, S. C.: Methane emissions from natural gas infrastructure and
use in the urban region of Boston, Massachusetts, P. Natl. Acad. Sci. USA,
112, 1941–1946, <ext-link xlink:href="https://doi.org/10.1073/pnas.1416261112" ext-link-type="DOI">10.1073/pnas.1416261112</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib23"><label>23</label><?label 1?><mixed-citation>Miller, S. M., Michalak, A. M., Detmers, R. R., Hasekamp, O. P., Bruhwiler,
L. M. P., and Schwietezke, S.: China's coal mine methane regulations have not
curbed growing emissions, Nat. Commun., 10, 1–8,
<ext-link xlink:href="https://doi.org/10.1038/s41558-019-0432-x" ext-link-type="DOI">10.1038/s41558-019-0432-x</ext-link>, 2019.</mixed-citation></ref>
      <ref id="bib1.bib24"><label>24</label><?label 1?><mixed-citation>Nisbet, E. G., Dlugokencky, E. J., Manning, M. R., Lowry, D., Fisher, R. E.,
France, J. L., Michel, S. E., Miller, J. B., White, J. W. C., Vaughn, B.,
Bousquet, P., Pyle, J. A., Warwick, N. J., Cain, M., Brownlow, R., Zazzeri,
G., Lanoiselle, M., Manning, A. C. Gloor, E., Worthy, D. E. J., Brunke, E. G.,
Labuschagne, C., Wolff, E. W., and Ganesan, A. L.: Rising atmospheric methane:
2007–2014 growth and isotopic shift, Global Biogeochem. Cy., 30,
1356–1370, <ext-link xlink:href="https://doi.org/10.1002/2016GB005406" ext-link-type="DOI">10.1002/2016GB005406</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib25"><label>25</label><?label 1?><mixed-citation>Nisbet, E. G., Manning, M. R., Dlugokencky, E. J., Fisher, R. E., Lowry, D.,
Michel, S. E., Myhre, C. L., Platt, S. M., Allen, G., Bousquet, P., Brownlow,
R., Cain, M., France, J. L., Hermansen, O., Hossaini, R., Jones, A. E, Levin,
I., Manning, A. C., Myhre, G., Pyle, J. A., Vaughn, B. H., Warwich, N. J., and
White, J. W. C.: Very strong atmospheric methane growth in the 4 years
2014–2017: Implications for the Paris Agreement, Global Biogeochem.
Cy., 33, 318–342, <ext-link xlink:href="https://doi.org/10.1029/2018GB006009" ext-link-type="DOI">10.1029/2018GB006009</ext-link>, 2019.</mixed-citation></ref>
      <ref id="bib1.bib26"><label>26</label><?label 1?><mixed-citation>Osborn, S. G. and McIntosh, J. C.:   Chemical and isotopic tracers of the
contribution of microbial gas in Devonian organic-rich shales and reservoir
sandstones, northern Appalachian Basin, Appl. Geochem., 25, 456–471,
<ext-link xlink:href="https://doi.org/10.1016/j.apgeochem.2010.01.001" ext-link-type="DOI">10.1016/j.apgeochem.2010.01.001</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib27"><label>27</label><?label 1?><mixed-citation>Pétron, G., Karion, A., Sweeney, C., Miller, B., Montzka, S. A., Frost,
G.J., Trainer, M., Tans, P., Andrews, A., Kofler, J., Helming, D., Guenther,
D., Dlugokencky, E., Lang, P., Newberger, T., Wolter, S., Hall, B., Novelli,
P., Brewer, R., Conley, S., Hardesty, M., Banta, R., White, A., Noone, D.,
Wolfe, D., and Schnell, R.: A new look at methane and nonmethane hydrocarbon
emissions from oil and natural gas operations in the Colorado
Denver-Julesburg Basin, J. Geophys. Res.-Atmos., 119, 6836–6852,
<ext-link xlink:href="https://doi.org/10.1002/2013JD021272" ext-link-type="DOI">10.1002/2013JD021272</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib28"><label>28</label><?label 1?><mixed-citation>Rice, A. L., Butenhoff, C. L., Tema, D. G., Florian, H. R., Khalil, M. A. K., and Rasmussen, R. A.: Atmospheric methane isotopic record
favors fossil sources flat in 1980s and 1990s with recent increase, P. Natl.
Acad. Sci. USA,  13, 10791–10796, <ext-link xlink:href="https://doi.org/10.1073/pnas.1522923113" ext-link-type="DOI">10.1073/pnas.1522923113</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib29"><label>29</label><?label 1?><mixed-citation>Rodriguez, N. D. and Philp, R. P.: Geochemical characterization of gases from
the Mississippian Barnett shale, Fort Worth Basin, Texas, AAPG Bull.,  94,
1641–56, <ext-link xlink:href="https://doi.org/10.1306/04061009119" ext-link-type="DOI">10.1306/04061009119</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib30"><label>30</label><?label 1?><mixed-citation>Rooze, J., Egger, M., Tsandev, I., and Slomp, C. P.: Iron-dependent anaerobic
oxidation of methane in coastal surface sediments: Potential controls and
impact, Limnol. Oceanogr.,  61, S267–S282, <ext-link xlink:href="https://doi.org/10.1002/lno.10275" ext-link-type="DOI">10.1002/lno.10275</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib31"><label>31</label><?label 1?><mixed-citation>Schaefer, H., Mikaloff-Fletcher, S. E., Veidt, C., Lassey, K. R., Brailsford,
G. W., Bromley, T. M., Dlubokencky, E. J., Michel, S. E., Miller, J. B., Levin,
I., Lowe, D. C., Martin, R. J., Vaugn, B. H., and White, J. W. C.: A 21st century
shift from fossil-fuel to biogenic methane emissions indicated by
<inline-formula><mml:math id="M145" display="inline"><mml:mrow class="chem"><mml:msup><mml:mi/><mml:mn mathvariant="normal">13</mml:mn></mml:msup><mml:msub><mml:mi mathvariant="normal">CH</mml:mi><mml:mn mathvariant="normal">4</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, Science,  352, 80–84, <ext-link xlink:href="https://doi.org/10.1126/science.aad2705" ext-link-type="DOI">10.1126/science.aad2705</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib32"><label>32</label><?label 1?><mixed-citation>Schlegel, M. E., McIntosh, J. C., Bates, B. L., Kirk, M. F., and Martini, A. M.:
Comparison of fluid geochemistry and microbiology of multiple organic-rich
reservoirs in the Illinois Basin, USA: Evidence for controls on
methanogenesis and microbial transport, Geochim. Cosmochim. Ac.,  75,
1903–1919, <ext-link xlink:href="https://doi.org/10.1016/j.gca.2011.01.016" ext-link-type="DOI">10.1016/j.gca.2011.01.016</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib33"><label>33</label><?label 1?><mixed-citation>Schneising, O., Burrows, J. P., Dickerson, R. R., Buchwitz, M., Reuter, M.,
and Bovensmann, H.: Remote sensing of fugitive emissions from oil and gas
production in North American tight geological formations, Earth's Future, 2,
548–558, <ext-link xlink:href="https://doi.org/10.1002/2014EF000265" ext-link-type="DOI">10.1002/2014EF000265</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib34"><label>34</label><?label 1?><mixed-citation>Schoell, M., Lefever, J. A., and Dow, W.: Use of maturity-related changes in
gas isotopes in production and exploration of Bakken shale plays, AAPG
Search and Discovery Article no. 90122 ©2011, AAPG Hedberg
Conference, 5–10 December 2010, Austin, Texas, available at: <uri>http://www.searchanddiscovery.com/abstracts/pdf/2011/hedberg-beijing/abstracts/ndx_schoell.pdf</uri> (last access: 27 June 2019), 2011.</mixed-citation></ref>
      <ref id="bib1.bib35"><label>35</label><?label 1?><mixed-citation>Schwietzke, S., Sherwood, O. A., Bruhwiler, L. M. P., Miller, J. B., Etiiope,
G., Dlugokencky, E. J., Michel, S. E., Arling, V. A., Vaughn, B. H.,
White, J. W. C., and Tans, P. P.: Upward revision of global fossil fuel methane
emissions based on isotope database, Nature, 538, 88–91,
<ext-link xlink:href="https://doi.org/10.1038/nature19797" ext-link-type="DOI">10.1038/nature19797</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib36"><label>36</label><?label 1?><mixed-citation>Sherwood, O. A., Schwietzke, S., Arling, V. A., and Etiope, G.: Global Inventory of Gas Geochemistry Data from Fossil Fuel, Microbial and Burning Sources, version 2017, Earth Syst. Sci. Data, 9, 63–656, <ext-link xlink:href="https://doi.org/10.5194/essd-9-639-2017" ext-link-type="DOI">10.5194/essd-9-639-2017</ext-link>, 2017.</mixed-citation></ref>
      <ref id="bib1.bib37"><label>37</label><?label 1?><mixed-citation>Shindell, D.: The social cost of atmospheric release, Climatic Change, 130,
313–326, <ext-link xlink:href="https://doi.org/10.1007/s10584-015-1343-0" ext-link-type="DOI">10.1007/s10584-015-1343-0</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib38"><label>38</label><?label 1?><mixed-citation>Shindell, D., Kuylenstierna, J. C., Vignati, E., van Dingenen, R., Amann, M.,
Klimont, Z., Anenberg, S. C., Muller, N., Janssens-Maenhout, G., Raes, R.,
Schwartz, J. Falvegi, G., Pozzoli, L., Kupiainent, K., Höglund-Isaksson,
L., Emberson, L., Streets, D. Ramanathan, V., Kicks, K., Oanh, N. T., Milly.,
G., Williams, M., Demkine, V., and Fowler, D.: Simultaneously mitigating
near-term climate change and improving human health and food security,
Science, 335, 183–189, <ext-link xlink:href="https://doi.org/10.1126/science.1210026" ext-link-type="DOI">10.1126/science.1210026</ext-link>, 2012.</mixed-citation></ref>
      <?pagebreak page3046?><ref id="bib1.bib39"><label>39</label><?label 1?><mixed-citation>Tilley, B. and Muehlenbachs, K.: Isotope reversals and universal stages and
trends of gas maturation in sealed, self-contained petroleum systems, Chem.
Geol., 339, 194–204, <ext-link xlink:href="https://doi.org/10.1016/j.chemgeo.2012.08.002" ext-link-type="DOI">10.1016/j.chemgeo.2012.08.002</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib40"><label>40</label><?label 1?><mixed-citation>Tilley, B., McLellan, S., Hiebert, S., Quartero, B., Veilleux, B., and
Muehlenbachs, K.: Gas isotope reversals in fractured gas reservoirs of the
western Canadian Foothills: Mature shale gases in disguise, AAPG Bull., 95,
1399–1422, <ext-link xlink:href="https://doi.org/10.1306/01031110103" ext-link-type="DOI">10.1306/01031110103</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib41"><label>41</label><?label 1?><mixed-citation>Townsend-Small, A., Marrero, J. E., Lyon, D. R., Simpson, I. J., Meinhardi, S.,
and Blake, D. R.: Integrating source apportionment tracers into a bottom-up
inventory of methane emissions in the Barnett shale hydraulic fracturing
region, Environ. Sci. Technol., 49, 8175–8182, <ext-link xlink:href="https://doi.org/10.1021/acs.est.5b00057" ext-link-type="DOI">10.1021/acs.est.5b00057</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib42"><label>42</label><?label 1?><mixed-citation>Turner, A. J., Jacob, D. J., Benmergui, J., Wofsy, S. C., Maasakker, J. D.,
Butz, A., Haekamp, O., and Biraud, S. C.: A large increase in US methane
emissions over the past decade inferred from satellite data and surface
observations, Geophys. Res. Lett., 43, 2218–2224, <ext-link xlink:href="https://doi.org/10.1002/2016GL067987" ext-link-type="DOI">10.1002/2016GL067987</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib43"><label>43</label><?label 1?><mixed-citation>
Turner, A. J., Frankenberg, C., Wennber, P. O., and Jacob, D. J.: Ambiguity in
the causes for decadal trends in atmospheric methane and hydroxyl, P. Natl.
Acad. Sci. USA, 114, 5367–5372,  2017.</mixed-citation></ref>
      <ref id="bib1.bib44"><label>44</label><?label 1?><mixed-citation>Vaughn, T. L., Bella, C. S., Picering, C. K., Schwietzke, S., Heath, G. A.,
Pétron, G., Zimmerle, D. J., Schnell, R. C., and Nummedal, D.: Temporal
variability largely explains top-down/bottom-up difference in methane
emission estimates from a natural gas production region, P. Natl. Acad. Sci.
USA, 115, 11712–11717, <ext-link xlink:href="https://doi.org/10.1073/pnas.1805687115" ext-link-type="DOI">10.1073/pnas.1805687115</ext-link>, 2018.
</mixed-citation></ref><?xmltex \hack{\newpage}?>
      <ref id="bib1.bib45"><label>45</label><?label 1?><mixed-citation>Whelan, J. K., Oremland, R., Tarata, M., Smith, R., Howarth, R., and Lee, C.: Evidence for sulfate reducing and methane producing microorganisms in
sediments from sites 618, 619, and 622, Reports of the Deep-Sea Drilling
Project, 47, 767–775, <ext-link xlink:href="https://doi.org/10.2973/dsdp.proc.96.147.1986" ext-link-type="DOI">10.2973/dsdp.proc.96.147.1986</ext-link>, 1986.</mixed-citation></ref>
      <ref id="bib1.bib46"><label>46</label><?label 1?><mixed-citation>Worden, J. R., Bloom, A. A., Pandey, S., Jiang, Z., Worden, H. M., Walter,
T. W., Houweling, S., and Röckmann, T.: Reduced biomass burning emissions
reconcile conflicting estimates of the post-2006 atmospheric methane budget,
Nat. Commun., 8, 2227, <ext-link xlink:href="https://doi.org/10.1038/s41467-017-02246-0" ext-link-type="DOI">10.1038/s41467-017-02246-0</ext-link>, 2017.</mixed-citation></ref>
      <ref id="bib1.bib47"><label>47</label><?label 1?><mixed-citation>Wunch, D., Toon, G. C., Hedelius, J. K., Vizenor, N., Roehl, C. M., Saad, K. M., Blavier, J.-F. L., Blake, D. R., and Wennberg, P. O.: Quantifying the loss of processed natural gas within California's South Coast Air Basin using long-term measurements of ethane and methane, Atmos. Chem. Phys., 16, 14091–14105, <ext-link xlink:href="https://doi.org/10.5194/acp-16-14091-2016" ext-link-type="DOI">10.5194/acp-16-14091-2016</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib48"><label>48</label><?label 1?><mixed-citation>Zumberge, J., Ferworn, K., and Brown, S.: Isotopic reversal (“rollover”)
in shale gases produced from the Mississippian Barnett and Fayetteville
formations, Mar. Petrol. Geol., 31, 43–52, <ext-link xlink:href="https://doi.org/10.1016/j.marpetgeo.2011.06.009" ext-link-type="DOI">10.1016/j.marpetgeo.2011.06.009</ext-link>, 2012.</mixed-citation></ref>

  </ref-list></back>
    <!--<article-title-html>Ideas and perspectives: is shale gas a major driver of recent increase in global atmospheric methane?</article-title-html>
<abstract-html><p>Methane has been rising rapidly in the atmosphere over the past
decade, contributing to global climate change. Unlike the late 20th
century when the rise in atmospheric methane was accompanied by an
enrichment in the heavier carbon stable isotope (<sup>13</sup>C) of methane,
methane in recent years has become more depleted in <sup>13</sup>C. This depletion
has been widely interpreted as indicating a primarily biogenic source for the
increased methane. Here we show that part of the change may instead be
associated with emissions from shale-gas and shale-oil development. Previous
studies have not explicitly considered shale gas, even though most of the
increase in natural gas production globally over the past decade is from
shale gas.
The methane in shale gas is somewhat depleted in <sup>13</sup>C relative to
conventional natural gas. Correcting earlier analyses for this difference,
we conclude that shale-gas production in North America over the past decade
may have contributed more than half of all of the increased emissions from
fossil fuels globally and approximately one-third of the total increased
emissions from all sources globally over the past decade.</p></abstract-html>
<ref-html id="bib1.bib1"><label>1</label><mixed-citation>
Alvarez, R. A., Zavalao-Araiza, D., Lyon, D. R., Allen, D. T., Barkley, Z. R.,
Brandt, A. R., Davis, K. J., Herndon, S. C., Jacob, D. J., Karion, A., Korts,
E. A., Lamb, B. K., Lauvaux, T., Maasakkers, J. D., Marchese, A. J., Omara, M.,
Pacala, J. W., Peiachl, J., Robinson, A. J., Shepson, P. B., Sweeney, C.,
Townsend-Small, A., Wofsy, S. C., and Hamburg, S. P.: Assessment of methane
emissions from the U.S. oil and gas supply chain, Science,  361, 186–188,
<a href="https://doi.org/10.1126/science.aar7204" target="_blank">https://doi.org/10.1126/science.aar7204</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib2"><label>2</label><mixed-citation>
Baldassare, F. J., McCaffrey, M. A., and Harper, J. A.: A geochemical context
for stray gas investigations in the northern Appalachian Basin: Implications
of analyses of natural gases from Neogene-through Devonian-age strata, AAPG
Bull., 98, 341–372, <a href="https://doi.org/10.1306/06111312178" target="_blank">https://doi.org/10.1306/06111312178</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib3"><label>3</label><mixed-citation>
Botner, E. C., Townsend-Small, A., Nash, D. B.,  Xu, X., Schimmelmann, A., and
Miller, J. H.: Monitoring concentration and isotopic composition of methane
in groundwater in the Utica Shale hydraulic fracturing region of Ohio,
Environ. Monit. Assess., 190, 322–337, <a href="https://doi.org/10.1007/s10661-018-6696-1" target="_blank">https://doi.org/10.1007/s10661-018-6696-1</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib4"><label>4</label><mixed-citation>
Burruss, R. C. and Laughrey, C. D.: Carbon and hydrogen isotopic reversals in
deep basin gas: evidence for limits to the stability of hydrocarbons,
Org. Geochem., 41, 1285–1296, <a href="https://doi.org/10.1016/j.orggeochem.2010.09.008" target="_blank">https://doi.org/10.1016/j.orggeochem.2010.09.008</a>,
2010.
</mixed-citation></ref-html>
<ref-html id="bib1.bib5"><label>5</label><mixed-citation>
Caulton, D. R., Shepson, P. D., Santoro, R. L., Sparks, J. P., Howarth, R. W.,
Ingraffea, A., Camaliza, M. O., Sweeney, C., Karion, A., Davis, K. J., Stirm,
B. H., Montzka, S. A., and   Miller, B.: Toward a better understanding and
quantification of methane emissions from shale gas development, P. Natl.
Acad. Sci. USA,  111, 6237–6242, <a href="https://doi.org/10.1073/pnas.1316546111" target="_blank">https://doi.org/10.1073/pnas.1316546111</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib6"><label>6</label><mixed-citation>
EIA: Shale gas and tight oil and commercially produced in just four
countries, Energy Information Administration, US Department of Energy,
available at: <a href="https://www.eia.gov/todayinenergy/detail.php?id=19991" target="_blank">https://www.eia.gov/todayinenergy/detail.php?id=19991</a> (last access: 14 September 2018), 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib7"><label>7</label><mixed-citation>
EIA: Shale gas production drives world natural gas production
growth, Energy Information Administration, US Department of Energy,
available at: <a href="https://www.eia.gov/todayinenergy/detail.php?id=27512" target="_blank">https://www.eia.gov/todayinenergy/detail.php?id=27512</a> (last access: 12 September 2018), 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib8"><label>8</label><mixed-citation>
EIA: Table 1.2, World crude oil production 1960–2017, Monthly energy review,
June 2018, Energy Information Administration, US Department of Energy, 1–244,
2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib9"><label>9</label><mixed-citation>
Golding, S. D., Boreham, C. J., and Esterle, J. S.: Stable isotope geochemistry
of coal bed and shale gas and related production waters: A review, Int. J.
Coal Geolog., 120, 24–40, <a href="https://doi.org/10.1016/j.coal.2013.09.001" target="_blank">https://doi.org/10.1016/j.coal.2013.09.001</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib10"><label>10</label><mixed-citation>
Hao, F. and Zou, H.: Cause of shale gas geochemical anomalies and
mechanisms for gas enrichment and depletion in high-maturity shales, Mar.
Petrol. Geol., 44, 1–12, <a href="https://doi.org/10.1016/j.marpetgeo.2013.03.005" target="_blank">https://doi.org/10.1016/j.marpetgeo.2013.03.005</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib11"><label>11</label><mixed-citation>
Howarth, R. W.: A bridge to nowhere: Methane emissions and the greenhouse gas
footprint of natural gas, Energy Sci. Eng., 2, 47–60, <a href="https://doi.org/10.1002/ese3.35" target="_blank">https://doi.org/10.1002/ese3.35</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib12"><label>12</label><mixed-citation>
Howarth, R. W., Santoro, R., and Ingraffea, A.: Methane and the greenhouse
gas footprint of natural gas from shale formations, Clim. Change Lett.,
106, 679–690, <a href="https://doi.org/10.1007/s10584-011-0061-5" target="_blank">https://doi.org/10.1007/s10584-011-0061-5</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib13"><label>13</label><mixed-citation>
IEA: World Energy Outlook, International Energy Agency, available at: <a href="https://webstore.iea.org/world-energy-outlook-2008" target="_blank">https://webstore.iea.org/world-energy-outlook-2008</a>
(last access: 12 September 2018), 2008.
</mixed-citation></ref-html>
<ref-html id="bib1.bib14"><label>14</label><mixed-citation>
IEA: Key World Energy Statistics, International Energy Agency, available at: <a href="https://www.iea.org/publications/freepublications/publication/KeyWorld2017.pdf" target="_blank">https://www.iea.org/publications/freepublications/publication/KeyWorld2017.pdf</a> (last access: 12 September 2018), 2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib15"><label>15</label><mixed-citation>
IPCC: Climate Change 2013: The Physical Science Basis. Contribution of
Working Group I to the Fifth Assessment Report of the Intergovernmental
Panel on Climate Change, Intergovernmental Panel on Climate Change, chap. 8, 659–740, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib16"><label>16</label><mixed-citation>
IPCC: Summary for Policymakers, in: Global warming of 1.5&thinsp;°C. An
IPCC Special Report on the impacts of global warming of 1.5&thinsp;°C
above pre-industrial levels and related global greenhouse gas emission
pathways, in the context of strengthening the global response to the threat
of climate change, sustainable development, and efforts to eradicate
poverty, Intergovernmental Panel on Climate Change, available at: <a href="http://www.ipcc.ch/report/sr15/" target="_blank">http://www.ipcc.ch/report/sr15/</a> (last access: 29 March 2019), 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib17"><label>17</label><mixed-citation>
Jacobson, M. Z., Howarth, R. W., Delucchi, M. A., Scobies, S. R., Barth,
J. M., Dvorak, M. J., Klevze, M., Katkhuda, H., Miranda, B., Chowdhury, N. A.,
Jones, R., Plano, L., and  Ingraffea, A. R.: Examining the feasibility of
converting New York State's all-purpose energy infrastructure to one using
wind, water, and sunlight, Energ. Policy, 57,  585–601, <a href="https://doi.org/10.1016/j.enpol.2013.02.036" target="_blank">https://doi.org/10.1016/j.enpol.2013.02.036</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib18"><label>18</label><mixed-citation>
Karion, A., Sweeney, C., Pétron, G., Frost, G., Hardesty, R. M., Kofler,
J., Miller, B. R., Newberger, T., Wolter, S., Banta, R., and Brewer, A.:
Methane emissions estimate from airborne measurements over a western United
States natural gas field, Geophys. Res. Lett., 40, 4393–4397,
<a href="https://doi.org/10.1002/grl.50811" target="_blank">https://doi.org/10.1002/grl.50811</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib19"><label>19</label><mixed-citation>
Lamb, B. K., Cambaliza, M. O. L., Davis, K. J., Edburg, S. L., Ferrara, T. W.,
Floerchinger, C., Heimburger, A. M. F., Herndon, S., Lauvaux, T., Lavoie, T.,
Lyon, D. R., Miles, N., Prasad, K. R., Richardson, S., Roscioli, J. R., Salmon,
O. E. Shepson, P. B., Stirm, B. H., and Whetstone, J.: Direct and indirect
measurements and modeling of methane emissions in Indianapolis, Indiana,
Environ. Sci. Technol., 50, 8910–8917, <a href="https://doi.org/10.1021/acs.est.6b01198" target="_blank">https://doi.org/10.1021/acs.est.6b01198</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib20"><label>20</label><mixed-citation>
Martini, A. M., Walter, L. M., Budai, J. M., Ku, T. C. W., Kaiser, C. J., and
Schoell, M.: Genetic and temporal relations between formation waters and
biogenic methane: Upper Devonian Antrim Shale, Michigan Basin, USA, Geochim.
Cosmochim. Ac., 62, 1699–1720, 1998.
</mixed-citation></ref-html>
<ref-html id="bib1.bib21"><label>21</label><mixed-citation>
McIntosh, J. C., Walter, L. M., and Martini, A. M.: Pleistocene recharge to
mid-continent basins: effects on salinity structure and microbial gas
generation, Geochim. Cosmochim. Ac., 66, 1681–1700,
<a href="https://doi.org/10.1016/S0016-7037(01)00885-7" target="_blank">https://doi.org/10.1016/S0016-7037(01)00885-7</a>, 2002.
</mixed-citation></ref-html>
<ref-html id="bib1.bib22"><label>22</label><mixed-citation>
McKain, K., Down, A., Raciti, S. M., Budney, J., Hutyra, L. R., Floerchinger,
C., Herndon, S. C., Nehrkorn, T., Zahniser, M. S., Jackson, R. B., Phillips,
N., and Wofsy, S. C.: Methane emissions from natural gas infrastructure and
use in the urban region of Boston, Massachusetts, P. Natl. Acad. Sci. USA,
112, 1941–1946, <a href="https://doi.org/10.1073/pnas.1416261112" target="_blank">https://doi.org/10.1073/pnas.1416261112</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib23"><label>23</label><mixed-citation>
Miller, S. M., Michalak, A. M., Detmers, R. R., Hasekamp, O. P., Bruhwiler,
L. M. P., and Schwietezke, S.: China's coal mine methane regulations have not
curbed growing emissions, Nat. Commun., 10, 1–8,
<a href="https://doi.org/10.1038/s41558-019-0432-x" target="_blank">https://doi.org/10.1038/s41558-019-0432-x</a>, 2019.
</mixed-citation></ref-html>
<ref-html id="bib1.bib24"><label>24</label><mixed-citation>
Nisbet, E. G., Dlugokencky, E. J., Manning, M. R., Lowry, D., Fisher, R. E.,
France, J. L., Michel, S. E., Miller, J. B., White, J. W. C., Vaughn, B.,
Bousquet, P., Pyle, J. A., Warwick, N. J., Cain, M., Brownlow, R., Zazzeri,
G., Lanoiselle, M., Manning, A. C. Gloor, E., Worthy, D. E. J., Brunke, E. G.,
Labuschagne, C., Wolff, E. W., and Ganesan, A. L.: Rising atmospheric methane:
2007–2014 growth and isotopic shift, Global Biogeochem. Cy., 30,
1356–1370, <a href="https://doi.org/10.1002/2016GB005406" target="_blank">https://doi.org/10.1002/2016GB005406</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib25"><label>25</label><mixed-citation>
Nisbet, E. G., Manning, M. R., Dlugokencky, E. J., Fisher, R. E., Lowry, D.,
Michel, S. E., Myhre, C. L., Platt, S. M., Allen, G., Bousquet, P., Brownlow,
R., Cain, M., France, J. L., Hermansen, O., Hossaini, R., Jones, A. E, Levin,
I., Manning, A. C., Myhre, G., Pyle, J. A., Vaughn, B. H., Warwich, N. J., and
White, J. W. C.: Very strong atmospheric methane growth in the 4 years
2014–2017: Implications for the Paris Agreement, Global Biogeochem.
Cy., 33, 318–342, <a href="https://doi.org/10.1029/2018GB006009" target="_blank">https://doi.org/10.1029/2018GB006009</a>, 2019.
</mixed-citation></ref-html>
<ref-html id="bib1.bib26"><label>26</label><mixed-citation>
Osborn, S. G. and McIntosh, J. C.:   Chemical and isotopic tracers of the
contribution of microbial gas in Devonian organic-rich shales and reservoir
sandstones, northern Appalachian Basin, Appl. Geochem., 25, 456–471,
<a href="https://doi.org/10.1016/j.apgeochem.2010.01.001" target="_blank">https://doi.org/10.1016/j.apgeochem.2010.01.001</a>, 2010.
</mixed-citation></ref-html>
<ref-html id="bib1.bib27"><label>27</label><mixed-citation>
Pétron, G., Karion, A., Sweeney, C., Miller, B., Montzka, S. A., Frost,
G.J., Trainer, M., Tans, P., Andrews, A., Kofler, J., Helming, D., Guenther,
D., Dlugokencky, E., Lang, P., Newberger, T., Wolter, S., Hall, B., Novelli,
P., Brewer, R., Conley, S., Hardesty, M., Banta, R., White, A., Noone, D.,
Wolfe, D., and Schnell, R.: A new look at methane and nonmethane hydrocarbon
emissions from oil and natural gas operations in the Colorado
Denver-Julesburg Basin, J. Geophys. Res.-Atmos., 119, 6836–6852,
<a href="https://doi.org/10.1002/2013JD021272" target="_blank">https://doi.org/10.1002/2013JD021272</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib28"><label>28</label><mixed-citation>
Rice, A. L., Butenhoff, C. L., Tema, D. G., Florian, H. R., Khalil, M. A. K., and Rasmussen, R. A.: Atmospheric methane isotopic record
favors fossil sources flat in 1980s and 1990s with recent increase, P. Natl.
Acad. Sci. USA,  13, 10791–10796, <a href="https://doi.org/10.1073/pnas.1522923113" target="_blank">https://doi.org/10.1073/pnas.1522923113</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib29"><label>29</label><mixed-citation>
Rodriguez, N. D. and Philp, R. P.: Geochemical characterization of gases from
the Mississippian Barnett shale, Fort Worth Basin, Texas, AAPG Bull.,  94,
1641–56, <a href="https://doi.org/10.1306/04061009119" target="_blank">https://doi.org/10.1306/04061009119</a>, 2010.
</mixed-citation></ref-html>
<ref-html id="bib1.bib30"><label>30</label><mixed-citation>
Rooze, J., Egger, M., Tsandev, I., and Slomp, C. P.: Iron-dependent anaerobic
oxidation of methane in coastal surface sediments: Potential controls and
impact, Limnol. Oceanogr.,  61, S267–S282, <a href="https://doi.org/10.1002/lno.10275" target="_blank">https://doi.org/10.1002/lno.10275</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib31"><label>31</label><mixed-citation>
Schaefer, H., Mikaloff-Fletcher, S. E., Veidt, C., Lassey, K. R., Brailsford,
G. W., Bromley, T. M., Dlubokencky, E. J., Michel, S. E., Miller, J. B., Levin,
I., Lowe, D. C., Martin, R. J., Vaugn, B. H., and White, J. W. C.: A 21st century
shift from fossil-fuel to biogenic methane emissions indicated by
<sup>13</sup>CH<sub>4</sub>, Science,  352, 80–84, <a href="https://doi.org/10.1126/science.aad2705" target="_blank">https://doi.org/10.1126/science.aad2705</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib32"><label>32</label><mixed-citation>
Schlegel, M. E., McIntosh, J. C., Bates, B. L., Kirk, M. F., and Martini, A. M.:
Comparison of fluid geochemistry and microbiology of multiple organic-rich
reservoirs in the Illinois Basin, USA: Evidence for controls on
methanogenesis and microbial transport, Geochim. Cosmochim. Ac.,  75,
1903–1919, <a href="https://doi.org/10.1016/j.gca.2011.01.016" target="_blank">https://doi.org/10.1016/j.gca.2011.01.016</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib33"><label>33</label><mixed-citation>
Schneising, O., Burrows, J. P., Dickerson, R. R., Buchwitz, M., Reuter, M.,
and Bovensmann, H.: Remote sensing of fugitive emissions from oil and gas
production in North American tight geological formations, Earth's Future, 2,
548–558, <a href="https://doi.org/10.1002/2014EF000265" target="_blank">https://doi.org/10.1002/2014EF000265</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib34"><label>34</label><mixed-citation>
Schoell, M., Lefever, J. A., and Dow, W.: Use of maturity-related changes in
gas isotopes in production and exploration of Bakken shale plays, AAPG
Search and Discovery Article no. 90122 ©2011, AAPG Hedberg
Conference, 5–10 December 2010, Austin, Texas, available at: <a href="http://www.searchanddiscovery.com/abstracts/pdf/2011/hedberg-beijing/abstracts/ndx_schoell.pdf" target="_blank">http://www.searchanddiscovery.com/abstracts/pdf/2011/hedberg-beijing/abstracts/ndx_schoell.pdf</a> (last access: 27 June 2019), 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib35"><label>35</label><mixed-citation>
Schwietzke, S., Sherwood, O. A., Bruhwiler, L. M. P., Miller, J. B., Etiiope,
G., Dlugokencky, E. J., Michel, S. E., Arling, V. A., Vaughn, B. H.,
White, J. W. C., and Tans, P. P.: Upward revision of global fossil fuel methane
emissions based on isotope database, Nature, 538, 88–91,
<a href="https://doi.org/10.1038/nature19797" target="_blank">https://doi.org/10.1038/nature19797</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib36"><label>36</label><mixed-citation>
Sherwood, O. A., Schwietzke, S., Arling, V. A., and Etiope, G.: Global Inventory of Gas Geochemistry Data from Fossil Fuel, Microbial and Burning Sources, version 2017, Earth Syst. Sci. Data, 9, 63–656, <a href="https://doi.org/10.5194/essd-9-639-2017" target="_blank">https://doi.org/10.5194/essd-9-639-2017</a>, 2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib37"><label>37</label><mixed-citation>
Shindell, D.: The social cost of atmospheric release, Climatic Change, 130,
313–326, <a href="https://doi.org/10.1007/s10584-015-1343-0" target="_blank">https://doi.org/10.1007/s10584-015-1343-0</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib38"><label>38</label><mixed-citation>
Shindell, D., Kuylenstierna, J. C., Vignati, E., van Dingenen, R., Amann, M.,
Klimont, Z., Anenberg, S. C., Muller, N., Janssens-Maenhout, G., Raes, R.,
Schwartz, J. Falvegi, G., Pozzoli, L., Kupiainent, K., Höglund-Isaksson,
L., Emberson, L., Streets, D. Ramanathan, V., Kicks, K., Oanh, N. T., Milly.,
G., Williams, M., Demkine, V., and Fowler, D.: Simultaneously mitigating
near-term climate change and improving human health and food security,
Science, 335, 183–189, <a href="https://doi.org/10.1126/science.1210026" target="_blank">https://doi.org/10.1126/science.1210026</a>, 2012.
</mixed-citation></ref-html>
<ref-html id="bib1.bib39"><label>39</label><mixed-citation>
Tilley, B. and Muehlenbachs, K.: Isotope reversals and universal stages and
trends of gas maturation in sealed, self-contained petroleum systems, Chem.
Geol., 339, 194–204, <a href="https://doi.org/10.1016/j.chemgeo.2012.08.002" target="_blank">https://doi.org/10.1016/j.chemgeo.2012.08.002</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib40"><label>40</label><mixed-citation>
Tilley, B., McLellan, S., Hiebert, S., Quartero, B., Veilleux, B., and
Muehlenbachs, K.: Gas isotope reversals in fractured gas reservoirs of the
western Canadian Foothills: Mature shale gases in disguise, AAPG Bull., 95,
1399–1422, <a href="https://doi.org/10.1306/01031110103" target="_blank">https://doi.org/10.1306/01031110103</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib41"><label>41</label><mixed-citation>
Townsend-Small, A., Marrero, J. E., Lyon, D. R., Simpson, I. J., Meinhardi, S.,
and Blake, D. R.: Integrating source apportionment tracers into a bottom-up
inventory of methane emissions in the Barnett shale hydraulic fracturing
region, Environ. Sci. Technol., 49, 8175–8182, <a href="https://doi.org/10.1021/acs.est.5b00057" target="_blank">https://doi.org/10.1021/acs.est.5b00057</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib42"><label>42</label><mixed-citation>
Turner, A. J., Jacob, D. J., Benmergui, J., Wofsy, S. C., Maasakker, J. D.,
Butz, A., Haekamp, O., and Biraud, S. C.: A large increase in US methane
emissions over the past decade inferred from satellite data and surface
observations, Geophys. Res. Lett., 43, 2218–2224, <a href="https://doi.org/10.1002/2016GL067987" target="_blank">https://doi.org/10.1002/2016GL067987</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib43"><label>43</label><mixed-citation>
Turner, A. J., Frankenberg, C., Wennber, P. O., and Jacob, D. J.: Ambiguity in
the causes for decadal trends in atmospheric methane and hydroxyl, P. Natl.
Acad. Sci. USA, 114, 5367–5372,  2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib44"><label>44</label><mixed-citation>
Vaughn, T. L., Bella, C. S., Picering, C. K., Schwietzke, S., Heath, G. A.,
Pétron, G., Zimmerle, D. J., Schnell, R. C., and Nummedal, D.: Temporal
variability largely explains top-down/bottom-up difference in methane
emission estimates from a natural gas production region, P. Natl. Acad. Sci.
USA, 115, 11712–11717, <a href="https://doi.org/10.1073/pnas.1805687115" target="_blank">https://doi.org/10.1073/pnas.1805687115</a>, 2018.

</mixed-citation></ref-html>
<ref-html id="bib1.bib45"><label>45</label><mixed-citation>
Whelan, J. K., Oremland, R., Tarata, M., Smith, R., Howarth, R., and Lee, C.: Evidence for sulfate reducing and methane producing microorganisms in
sediments from sites 618, 619, and 622, Reports of the Deep-Sea Drilling
Project, 47, 767–775, <a href="https://doi.org/10.2973/dsdp.proc.96.147.1986" target="_blank">https://doi.org/10.2973/dsdp.proc.96.147.1986</a>, 1986.
</mixed-citation></ref-html>
<ref-html id="bib1.bib46"><label>46</label><mixed-citation>
Worden, J. R., Bloom, A. A., Pandey, S., Jiang, Z., Worden, H. M., Walter,
T. W., Houweling, S., and Röckmann, T.: Reduced biomass burning emissions
reconcile conflicting estimates of the post-2006 atmospheric methane budget,
Nat. Commun., 8, 2227, <a href="https://doi.org/10.1038/s41467-017-02246-0" target="_blank">https://doi.org/10.1038/s41467-017-02246-0</a>, 2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib47"><label>47</label><mixed-citation>
Wunch, D., Toon, G. C., Hedelius, J. K., Vizenor, N., Roehl, C. M., Saad, K. M., Blavier, J.-F. L., Blake, D. R., and Wennberg, P. O.: Quantifying the loss of processed natural gas within California's South Coast Air Basin using long-term measurements of ethane and methane, Atmos. Chem. Phys., 16, 14091–14105, <a href="https://doi.org/10.5194/acp-16-14091-2016" target="_blank">https://doi.org/10.5194/acp-16-14091-2016</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib48"><label>48</label><mixed-citation>
Zumberge, J., Ferworn, K., and Brown, S.: Isotopic reversal (“rollover”)
in shale gases produced from the Mississippian Barnett and Fayetteville
formations, Mar. Petrol. Geol., 31, 43–52, <a href="https://doi.org/10.1016/j.marpetgeo.2011.06.009" target="_blank">https://doi.org/10.1016/j.marpetgeo.2011.06.009</a>, 2012.
</mixed-citation></ref-html>--></article>
