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Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

Identifieur interne : 000075 ( Pmc/Curation ); précédent : 000074; suivant : 000076

Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

Auteurs : Henrik Drake [Suède] ; Mats E. Ström [Suède] ; Christine Heim [Allemagne] ; Curt Broman [Suède] ; Jan Ström [Finlande] ; Martin Whitehouse [Suède] ; Magnus Ivarsson [Suède] ; Sandra Siljeström [Suède] ; Peter Sjövall [Suède]

Source :

RBID : PMC:4432592

Abstract

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.


Url:
DOI: 10.1038/ncomms8020
PubMed: 25948095
PubMed Central: 4432592

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PMC:4432592

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<p>Precipitation of exceptionally
<sup>13</sup>
C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in
<sup>13</sup>
C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in
<sup>13</sup>
C (
<italic>δ</italic>
<sup>13</sup>
C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely
<sup>13</sup>
C-depleted carbonates ever reported, δ
<sup>13</sup>
C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.</p>
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</TEI>
<pmc article-type="research-article">
<pmc-dir>properties open_access</pmc-dir>
<front>
<journal-meta>
<journal-id journal-id-type="nlm-ta">Nat Commun</journal-id>
<journal-id journal-id-type="iso-abbrev">Nat Commun</journal-id>
<journal-title-group>
<journal-title>Nature Communications</journal-title>
</journal-title-group>
<issn pub-type="epub">2041-1723</issn>
<publisher>
<publisher-name>Nature Pub. Group</publisher-name>
</publisher>
</journal-meta>
<article-meta>
<article-id pub-id-type="pmid">25948095</article-id>
<article-id pub-id-type="pmc">4432592</article-id>
<article-id pub-id-type="pii">ncomms8020</article-id>
<article-id pub-id-type="doi">10.1038/ncomms8020</article-id>
<article-categories>
<subj-group subj-group-type="heading">
<subject>Article</subject>
</subj-group>
</article-categories>
<title-group>
<article-title>Extreme
<sup>13</sup>
C depletion of carbonates formed during oxidation of biogenic methane in fractured granite</article-title>
</title-group>
<contrib-group>
<contrib contrib-type="author">
<name>
<surname>Drake</surname>
<given-names>Henrik</given-names>
</name>
<xref ref-type="corresp" rid="c1">a</xref>
<xref ref-type="aff" rid="a1">1</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Åström</surname>
<given-names>Mats E.</given-names>
</name>
<xref ref-type="aff" rid="a1">1</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Heim</surname>
<given-names>Christine</given-names>
</name>
<xref ref-type="aff" rid="a2">2</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Broman</surname>
<given-names>Curt</given-names>
</name>
<xref ref-type="aff" rid="a3">3</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Åström</surname>
<given-names>Jan</given-names>
</name>
<xref ref-type="aff" rid="a4">4</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Whitehouse</surname>
<given-names>Martin</given-names>
</name>
<xref ref-type="aff" rid="a5">5</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Ivarsson</surname>
<given-names>Magnus</given-names>
</name>
<xref ref-type="aff" rid="a6">6</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Siljeström</surname>
<given-names>Sandra</given-names>
</name>
<xref ref-type="aff" rid="a7">7</xref>
</contrib>
<contrib contrib-type="author">
<name>
<surname>Sjövall</surname>
<given-names>Peter</given-names>
</name>
<xref ref-type="aff" rid="a7">7</xref>
</contrib>
<aff id="a1">
<label>1</label>
<institution>Department of Biology and Environmental Science, Linnæus University</institution>
, SE-39182 Kalmar,
<country>Sweden</country>
</aff>
<aff id="a2">
<label>2</label>
<institution>Department of Geobiology, Geoscience Centre Göttingen of the Georg-August University</institution>
, Goldschmidtstrasse 3, 37077 Göttingen,
<country>Germany</country>
</aff>
<aff id="a3">
<label>3</label>
<institution>Department of Geological Sciences, Stockholm University</institution>
, SE-106 91 Stockholm,
<country>Sweden</country>
</aff>
<aff id="a4">
<label>4</label>
<institution>CSC-IT Center for Science</institution>
, PO Box 405, FIN-02101 Esbo,
<country>Finland</country>
</aff>
<aff id="a5">
<label>5</label>
<institution>Laboratory for Isotope Geology, Swedish Museum of Natural History</institution>
, PO Box 50 007, SE-10405 Stockholm,
<country>Sweden</country>
</aff>
<aff id="a6">
<label>6</label>
<institution>Department of palaeobiology and the Nordic Center for Earth Evolution (NordCEE), Swedish Museum of Natural History</institution>
, PO Box 50 007, SE-10405 Stockholm,
<country>Sweden</country>
</aff>
<aff id="a7">
<label>7</label>
<institution>Department of Surfaces, Chemistry and Materials, SP Technical Research Institute of Sweden</institution>
, PO Box 857, SE-50115 Borås,
<country>Sweden</country>
</aff>
</contrib-group>
<author-notes>
<corresp id="c1">
<label>a</label>
<email>henrik.drake@lnu.se</email>
</corresp>
</author-notes>
<pub-date pub-type="epub">
<day>07</day>
<month>05</month>
<year>2015</year>
</pub-date>
<volume>6</volume>
<elocation-id>7020</elocation-id>
<history>
<date date-type="received">
<day>04</day>
<month>09</month>
<year>2014</year>
</date>
<date date-type="accepted">
<day>23</day>
<month>03</month>
<year>2015</year>
</date>
</history>
<permissions>
<copyright-statement>Copyright © 2015, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.</copyright-statement>
<copyright-year>2015</copyright-year>
<copyright-holder>Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.</copyright-holder>
<license license-type="open-access" xlink:href="http://creativecommons.org/licenses/by/4.0/">
<pmc-comment>author-paid</pmc-comment>
<license-p>This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit
<ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/4.0/">http://creativecommons.org/licenses/by/4.0/</ext-link>
</license-p>
</license>
</permissions>
<abstract>
<p>Precipitation of exceptionally
<sup>13</sup>
C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in
<sup>13</sup>
C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in
<sup>13</sup>
C (
<italic>δ</italic>
<sup>13</sup>
C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely
<sup>13</sup>
C-depleted carbonates ever reported, δ
<sup>13</sup>
C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.</p>
</abstract>
<abstract abstract-type="web-summary">
<p>
<inline-graphic id="i1" xlink:href="ncomms8020-i1.jpg"></inline-graphic>
Precipitation of
<sup>13</sup>
C-depleted authigenic carbonate is a tracer of sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Here, the authors present extremely
<sup>13</sup>
C-depleted carbonates from deep granitoid rocks suggesting the presence of microbial sulphate reducers and methane oxidisers.</p>
</abstract>
</article-meta>
</front>
<floats-group>
<fig id="f1">
<label>Figure 1</label>
<caption>
<title>Fracture and mineral characteristics.</title>
<p>(
<bold>a</bold>
) Drill core with an exposed fracture surface (scale in cm). (
<bold>b</bold>
,
<bold>c</bold>
) SEM images of crystals
<italic>in situ</italic>
on the fracture wall (scale bars, 500 μm). The calcite in
<bold>c</bold>
is formed via anaerobic oxidation of methane and is intergrown with pyrite formed in relation to bacterial sulphate reduction.</p>
</caption>
<graphic xlink:href="ncomms8020-f1"></graphic>
</fig>
<fig id="f2">
<label>Figure 2</label>
<caption>
<title>Depth-related variations of geochemical variables in the groundwater and in calcite.</title>
<p>(
<bold>a</bold>
) Sulphate and methane concentrations
<xref ref-type="bibr" rid="b34">34</xref>
in the groundwater. (
<bold>b</bold>
)
<italic>δ</italic>
<sup>13</sup>
C
<sub>calcite</sub>
and groundwater
<italic>δ</italic>
<sup>13</sup>
C
<sub>DIC</sub>
. (
<bold>c</bold>
)
<italic>δ</italic>
<sup>18</sup>
O
<sub>calcite</sub>
. Panel
<bold>c</bold>
includes a range for hypothetical calcite precipitated from the current groundwater at the same depth where the AOM- or methanogenesis-calcite coatings were collected. Equation 1,000 l
<italic></italic>
(Calcite−H
<sub>2</sub>
0)=18.03(10
<sup>3 </sup>
T
<sup>−1</sup>
)−32.42 (ref.
<xref ref-type="bibr" rid="b36">36</xref>
) is used to calculate the fractionation factor (
<italic>α</italic>
) between oxygen in water and calcite at borehole water temperatures of 5–20 °C (hence the range). (
<bold>d</bold>
)
<italic>δ</italic>
<sup>34</sup>
S values of pyrite in paragenesis with AOM-related crystals, together with pyrite in paragenesis with methanogenesis-related calcite and pyrite without any indicated methane relation
<xref ref-type="bibr" rid="b31">31</xref>
. For the stable isotope analyses, the symbol sizes are larger than the analytical uncertainties. Groundwater data are listed in
<xref ref-type="supplementary-material" rid="S1">Supplementary Table 2</xref>
and full stable carbon, oxygen and sulphur isotope data for calcite and pyrite in
<xref ref-type="supplementary-material" rid="S1">Supplementary Tables 1 and 3</xref>
.</p>
</caption>
<graphic xlink:href="ncomms8020-f2"></graphic>
</fig>
<fig id="f3">
<label>Figure 3</label>
<caption>
<title>Variation of stable isotope composition within different calcite and pyrite crystals.</title>
<p>Transects of SIMS analyses are shown in back-scattered SEM images above, and isotopic compositions corresponding to these analyses below. Growth direction of calcite is from left to right. (
<bold>a</bold>
) Calcite with episodic methanogenesis-related signature (positive
<italic>δ</italic>
<sup>13</sup>
C, blue symbol). This is the dominant appearance of methanogenesis-related calcite, related to
<italic>δ</italic>
<sup>18</sup>
O with marine-influenced signature followed by lighter
<italic>δ</italic>
<sup>13</sup>
C and
<italic>δ</italic>
<sup>18</sup>
O. (
<bold>b–e</bold>
) AOM-related calcite (green symbols) with typical associated increase in
<italic>δ</italic>
<sup>18</sup>
O values from the earlier growth zone (indicative of increased marine influence). (
<bold>d,e</bold>
) AOM-related calcite succeeded by calcite with significantly heavier
<italic>δ</italic>
<sup>13</sup>
C and lighter
<italic>δ</italic>
<sup>18</sup>
O (fresh water, with large glacial component, especially in
<bold>e</bold>
). (
<bold>f</bold>
)
<italic>δ</italic>
<sup>34</sup>
S evolution with growth from core to rim in pyrite from three different fractures. The symbol sizes are generally larger than the analytical uncertainties (except for
<italic>δ</italic>
<sup>18</sup>
O, where error bars are shown). Scale bars (
<bold>a</bold>
) 300 μm, (
<bold>b</bold>
) 200 μm, (
<bold>c</bold>
) 200 μm, (
<bold>d</bold>
) 100 μm, (
<bold>e</bold>
) 200 μm, (
<bold>f</bold>
) 50 μm.</p>
</caption>
<graphic xlink:href="ncomms8020-f3"></graphic>
</fig>
<fig id="f4">
<label>Figure 4</label>
<caption>
<title>Organic compounds detected in a calcite leachate (210 mg) from KLX03−623 m.</title>
<p>(
<bold>a</bold>
) GC–MS. Fatty acids (FA) observed with GC–MS can be separated into short-chain FA to a bacterial contribution (C
<sub>14</sub>
to C
<sub>19</sub>
), with
<italic>i</italic>
- and
<italic>ai</italic>
-C
<sub>15</sub>
;
<italic>10Me</italic>
-C
<sub>16</sub>
;
<italic>i</italic>
- and
<italic>ai</italic>
-C
<sub>17</sub>
being very common in SRB, and long-chain FA (C
<sub>20</sub>
to C
<sub>34</sub>
) that may represent a diagenetic signature of high plants. (
<bold>b</bold>
) ToF-SIMS spectrum revealing the presence of hopanoids, DAGE and ester-bound diacylglycerols (DGs). Exact masses and characteristic fragments observed are given in
<xref ref-type="supplementary-material" rid="S1">Supplementary Table 4</xref>
.</p>
</caption>
<graphic xlink:href="ncomms8020-f4"></graphic>
</fig>
<fig id="f5">
<label>Figure 5</label>
<caption>
<title>Schematic images of the processes in the fractures.</title>
<p>(
<bold>a</bold>
) An overview including typically near-vertical to vertical water-conducting fractures through which marine waters descended (width of view c. 1 km). (
<bold>b</bold>
) Conditions and (
<bold>c</bold>
) reactions occurring locally in open fractures (width of view in
<bold>b</bold>
is c. 700–800 μm). Sulphate-poor descending fluids containing the methane mix with a deeper sulphate-rich, bicarbonate-poor water. At this transition AOM occurs, involving bacterial sulphate reduction promoting pyrite precipitation and increased alkalinity triggering calcite formation. AOM occurs preferentially in microbial communities (black, degraded over time) at the fracture walls, and the incorporation of carbon into calcite is therefore dominated by products of the local AOM process, as shown by both the
<italic>δ</italic>
<sup>13</sup>
C values, and by the closed system conditions of the sulphate reduction (evidenced by the
<italic>δ</italic>
<sup>34</sup>
S evolution within the pyrites).</p>
</caption>
<graphic xlink:href="ncomms8020-f5"></graphic>
</fig>
</floats-group>
</pmc>
</record>

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