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doi: 10.1111/j.1365-3121.2009.00882.

Global hydrocarbon seep-carbonate precipitation correlates with


deep-water temperatures and eustatic sea-level fluctuations since
the Late Jurassic
Steffen Kiel
Institut für Geowissenschaften, Christian-Albrechts-Universität, Ludewig-Meyn-Str. 10, 24118 Kiel, Germany and Department of Paleobiology,
Smithsonian Natural History Museum, PO Box 37012, Washington, DC 20013-7012, USA

ABSTRACT
The anaerobic oxidation of methane (AOM) in marine sedi- hydrates decompose in deeper sediments, thereby increasing
ments, most obviously at cold seeps, is a major sink for this seepage and carbonate precipitation. Alternatively, low deep-
important greenhouse gas and is associated with the precip- water temperature facilitates gas hydrate formation on con-
itation of carbonates. The geological record of seep carbon- tinental slopes and may thereby increase methane availability
ates provides insights into the long-term dynamics of this for AOM-performing consortia and associated carbonate pre-
process. Since the Late Jurassic, rates of seep-carbonate cipitation. These correlations and their potential causes may
precipitation have been high during times of low sea levels be of interest for the modelling of global carbon budgets and
and cold deep-water temperatures, and vice versa. One of past and future climates.
possibility is that sea-level fall decreases the thickness of the
methane hydrate stability zone in the sediment so that gas Terra Nova, 21, 279–284, 2009

cycles their occurrence appears to that all formations contain an equal


Introduction
correlate with sea-level low-stands amount of seep carbonate. This is
Methane is an important greenhouse and cold periods (Teichert et al., admittedly a crude simplification but,
gas that influenced the global climate 2003; Watanabe et al., 2008) and it given the heterogeneous nature of the
in the geological past and will was suggested that the rate of seepage data, it is currently the most feasible
undoubtedly do so in the future is sensitive to pressure changes in- proxy.
(Maslin and Thomas, 2003). A major duced by the overlying water column
sink for methane in marine sediments (cf., Teichert et al., 2003). Using seep-
Seep-bearing formations vs. sea
is the anaerobic oxidation of methane carbonate-bearing rock formations as
level and deep-water temperature
(AOM) carried out by a microbial a proxy, I show in this article that this
consortium oxidising methane in a correlation also exists on a much To evaluate the relationships between
direct coupling with sulphate reduc- larger geological time-scale, from the seep-carbonate precipitation and long-
tion (Boetius et al., 2000). The pre- Late Jurassic to the Recent. Potential term fluctuations in sea level and deep-
cipitation of carbonate is a by-product reasons for this correlation are water temperature, the frequency
of this process, most obviously at discussed. distribution of seep-bearing rock for-
places known as cold seeps, where mations since the Late Jurassic was
flux rates of methane are high (Kulm compared with global sea-level and
Proxies and assumptions
et al., 1986; Peckmann et al., 2001). temperature curves. The basis for the
Seep carbonates are known from the To directly quantify the volume of comparison is an updated compilation
geological record (Fig. 1) and are an seep carbonate in the geological of seep-bearing rock formations from
archive of the history of methane record is not feasible, hence proxies Kiel and Little (2006). Updates include
oxidation in the geological past (Peck- have to be used and simplifications the exclusion of sites with typical seep
mann and Thiel, 2004). Recent have to be made. The most commonly macrofauna but without carbonate (i.e.
improvements in dating seep carbon- used proxies for rock volume in the in Majima et al., 2005) and the inclu-
ates indicate that they have not geological record are named forma- sion of non-fossiliferous seep carbon-
formed continuously through time: tions (Peters and Foote, 2001, 2002), ates (Fig. 2; see Table S1). The 66
during Pleistocene glacial–interglacial gap-bound sequences (Peters, 2005, formations were binned into 10-Ma
2008) and outcrop area (Smith et al., intervals from the present to 150 Ma
Correspondence: Steffen Kiel, Institut für
2001; Crampton et al., 2003). The ago. Each formation was counted once
Geowissenschaften, Christian-Albrechts-
latter two are not applicable in this for each time bin, regardless of the
Universität, Ludewig-Meyn-Str. 10, 24118 context because the relevant fossil number of individual seep deposits it
Kiel, Germany and Department of seep-carbonate occurrences have been contained. When a formation spanned
Paleobiology, Smithsonian Natural History reported under various scopes and more than one time bin the formation
Museum, PO Box 37012, Washington, DC conditions from 18 countries on five was counted for each time bin in which
20013-7012, USA. Tel.: +49 (0)431 880 continents. Thus, seep-carbonate- seep carbonates occur (see Supporting
2856; fax: +49 (0)431 880 4376; e-mail: bearing rock formations in a broad Information). The resulting frequency
steffen.kiel@gmx.de sense are used here. Doing so implies distribution is shown in Fig. 3. This

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Linking seep carbonates, sea level and temperature • S. Kiel Terra Nova, Vol 21, No. 4, 279–284
.............................................................................................................................................................
ceous but beyond 100 Ma ago they are
scarce or not available. Rather than
mixing the foraminifera data with
other proxies for deep-water tempera-
ture, such as high-latitude surface
temperatures derived from belemnite
fragmocones or glendonites (cf., Price,
1999; Price and Mutterlose, 2004), the
time span from 100 to 150 Ma ago has
been omitted from this analysis. The
data used here are the absolute tem-
peratures calculated for a non-glacial
world by Zachos et al. (2001) and
Huber et al. (2002). The value for each
10 Ma bin is the mean of the temper-
atures at its start, median and end
dates. The comparison (Fig. 3) shows a
significant correlation (SpearmanÕs
q = 0.01) between high numbers of
seep-bearing formations and low
Fig. 1 Two seep carbonate bodies (white arrows) in the Late Miocene Morai
deep-water temperatures.
Formation, western Hokkaido, Japan.

Significance of sampling
dataset was compared with the curve of formations correlate with low sea levels
first-order sea-level fluctuations pub- and vice versa. This negative correla- It may be argued that the frequency
lished by Haq et al. (1987). To facili- tion is statistically significant (Spear- distribution of the currently known
tate a numerical comparison, the manÕs q < 0.01). seep-bearing formations only inciden-
amplitude of this curve was divided Comparing the frequency distribu- tally correlates with the sea-level and
into 10 equally spaced intervals, with tion of seep-bearing formations with temperature curves and that future
the present sea level coded as zero and deep-water temperature, is temporally discoveries of seep-bearing formations
the maximum sea-level high stand, at limited. Oxygen isotope data obtained could change this result. To test this
c. 93 Ma, coded as 10. The mean value from benthic foraminifera from deep- hypothesis, the significance of the cor-
for each 10 Ma bin was calculated sea drill cores provide the most reliable relations was calculated with the
as (valuestart date+valuemedian date+ proxy for deep-water temperature. number of seep-bearing formations
valueend date) ⁄ 3. The comparison shows Such data are available for the Ceno- that were known each year from 1996
that high numbers of seep-bearing zoic and the larger part of the Creta- to 2008. The start date was chosen

Fig. 2 Map showing the geographical distribution of the Late Jurassic to Pleistocene seep-bearing formations used here. Numbers
correspond to those in Table S1.

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Terra Nova, Vol 21, No. 4, 279–284 S. Kiel • Linking seep carbonates, sea level and temperature
.............................................................................................................................................................
methane out of the underlying source

High
Eustatic sea level fluctuation rock, resulting in the precipitation of
more seep carbonate. This mechanism
should act on seepage at any water
14 depth on the continental slopes,
regardless of the geological age and
Seep-bearing formations

12 Deep-water temperature
depth of the source rock(s). It may thus
10 contribute to the observed higher
frequency of seep-carbonate-bearing
8

Low
formations during times of sea-level
6 low-stands. However, this scenario is
contradicted by suggestions that the
4 local tectonic regime is the major force
2
driving methane out of the source rock
(Hensen et al., 2004; Aiello, 2005).
0 Alternatively, temperature could
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
have an impact on methane flux into
Million years
a b the sulphate–methane transition zone
(SMTZ), where AOM actually takes
Fig. 3 Frequency distribution of seep-bearing formations since the Late Jurassic, place. The link may again be gas
binned into 10 Ma intervals. Black bars represent formations known in 1998; grey hydrate, which – when stable – might
bars represent the additional formations published in 1999–2003 (dark grey) and buffer fluctuating methane flux rates
2004–2008 (light grey). The sea-level curve shows first-order fluctuations after Haq in the uppermost 250 m of sediment
et al. (1987) (magnitude exaggerated). The deep-water temperature curve represents (cf., Boetius and Suess, 2004) as fol-
absolute temperatures calculated for a non-glacial world by Zachos et al. (2001) for lows: methane arriving at fluctuating
the Cenozoic and Huber et al. (2002) for the Cretaceous. (a) Inferred 50% drop in the
oceansÕ sulphate content (cf. Wortmann and Chernyavsky, 2007). (b) Onset of the
glaciation of Antarctica.
(a) 0.012

because since 1996 details on more than decomposition in deeper sediments.

Spearman’s ρ
twice as many new seep-bearing for- [This…] may then generate enhanced 0.01
mations have been published as time gas and fluid flow in the cold seep
bins used in this study (34 formations areasÕ. These mechanisms would result 0.008
vs. 15 time bins). Since 1996, the in the precipitation of fewer seep
correlations have always been statisti- carbonates during sea-level rises and
cally significant at levels well below the more seep carbonates during sea-level 0.006
critical point of q = 0.05 for both the falls. On larger geological time-scales,
sea-level and the temperature curves this scenario implies that seep-carbon- 96 98 00 02 04 06 08
19 19 20 20 20 20 20
(Fig. 4). Furthermore, standard regres- ate precipitation is enhanced during
sions show that the significance of both times of rapidly oscillating sea levels, (b)
correlations has increased with contin- because each individual sea-level fall 0.032
ued sampling (straight lines in Fig. 4). would result in the precipitation of
Spearman’s ρ

It is thus concluded that the correla- seep carbonate. In glacial times, the 0.024
tions shown here are unlikely to be a accumulation and melting of ice sheets
coincidental result of the current state caused by short-term climate changes 0.016
of research but reflect a real geological and Milankovitch cycles facilitated
phenomenon. oscillating sea levels (Hays et al., 0.008
1976). This could explain the coinci-
dence of the extreme increase in the 98 00 02 04 06 08
Discussion 96 20
number of seep-bearing formations 19 19 20 20 20 20
with the onset of the Antarctic glaci- Year
What might have caused the observed
correlations? For Pleistocene glacial– ation in the Late Eocene (Fig. 3; cf.,
Fig. 4 Statistical significance of the
interglacial cycles, Teichert et al. Zachos et al., 2001).
observed correlations with increased
(2003) suggested that increasing water Another way in which sea-level fluc- sampling. All values are better than
pressure on the plumbing system of tuations may influence methane flux q = 0.05; straight lines are the standard
the seep induced by a rising sea level rates is by controlling sediment load. regression showing that the significance
may inhibit the rise of fluids from the During times of low sea levels, more of the correlations increased with addi-
sediment. Furthermore, Teichert et al. sediment is deposited on the continen- tional sampling (lower q values indicate
(2003, p. 3855) also stated Ô...sea level tal slopes than during high-stands, higher statistical significance). (a) Cor-
lowering would shift the bottom of the when sedimentation on the shelves relation with sea-level fluctuations. (b)
gas hydrate stability zone into shal- prevails. It is possible that the Correlation with deep-water tempera-
lower depths followed by gas hydrate increased sediment load squeezes more ture.

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Linking seep carbonates, sea level and temperature • S. Kiel Terra Nova, Vol 21, No. 4, 279–284
.............................................................................................................................................................
rates in the hydrate stability zone is gas hydrate, thereby contributing to coupled to sulphate reduction. How-
enclosed in hydrates; continued sedi- the scarcity of seep carbonates during ever, even a major decrease in the
mentation moves the methane hy- this time. A potential argument oceansÕ sulphate content of perhaps
drates deeper into the sediment and against this hypothesis is that the 50% because of evaporite (gypsum)
ultimately out of the hydrate stability higher sea level would counter this deposition at c.120 Ma ago with a
zone; this results in their dissociation effect, because the higher water pres- subsequent return to previous levels
and the release of methane, thereby sure would enhance hydrate forma- at c. 95–75 Ma ago (cf., Paytan et al.,
providing a relatively constant source tion. But, as indicated in Fig. 5, a 2004; Wortmann and Chernyavsky,
of methane for AOM and associated temperature increase of only 1–2 C 2007), appears to have had no
carbonate precipitation in the SMTZ. will ÔcompensateÕ for the effect of a sea effect on seep-carbonate abundances
When high deep-water temperatures level 200 m higher than today, as (Fig. 3).
prevent gas hydrate formation, this assumed for the maximum flooding Clearly, factors other than those
buffering effect disappears and meth- of the Late Cretaceous (Hay, 2008). discussed in this article might also
ane arrives in the SMTZ at the Thus a rising sea level seems insuffi- have influenced seep-carbonate pre-
fluctuating rates at which it is expelled cient to counter the effect of temper- cipitation through Earth history, and
from the source rock. In this case, ature increase in driving the upper those discussed above might well have
more methane could potentially depth limit of hydrate formation acted in concert with as-yet-unknown
escape oxidation by AOM consortia, down the continental slopes. A poten- degrees of significance. However, it is
resulting in the precipitation of less tially important implication is that hoped that this first attempt to quan-
carbonate. The upper depth limit at under such conditions not only would tify methane seepage through Earth
which methane hydrates can form is gas hydrates fail to act as a methane history using geological data will
determined by the pressure (as sink but to some extent so also would inspire further investigations in this
imposed by the water depth) and the seep carbonates, contributing further field.
temperature (Fig. 5). Whereas in the to climate warming (see also Archer,
oceans today the upper depth limit of 2007). However, two observations
Conclusions
gas hydrate stability is around 500 m, contradict this scenario: (i) AOM
it would have been 1000–1500 m and associated seep-carbonate forma- Statistically relevant correlations
deeper in the Cretaceous greenhouse tion are known from areas without between the frequencies of seep-
climate (Fig. 5), leaving a significant underlying gas hydrates (Jensen et al., carbonate-bearing rock formations on
part of the continental slopes free of 1992; Hjelsteun et al., 1999; Peck- the one hand and sea-level fluctuations
mann et al., 2001) and (ii) AOM and deep-water temperature on the
100 consortia are known to adapt rapidly other hand are documented here for
to changing methane fluxes (Boetius the past 150 and 100 Ma, respectively.
and Wegener, 2008). High numbers of seep-carbonate-
Lastly, temperature may have an bearing formations correlate with low
impact on the microbial consortia sea levels and low deep-water tempera-
responsible for AOM. Nauhaus et al. tures, and vice versa, indicating that
500 Methane gas + water (2005) showed that ANME II Archaea sea-level fluctuations and deep-water
Water depth (m)

are more adapted to cold temperatures temperatures have an effect on the


than ANME I Archaea. ANME II rates of methane flux and ⁄ or oxidation
1000 Archaea have significantly higher cell- and the associated precipitation of
Gas hydrate b specific AOM rates than ANME I carbonate.
Archaea, and thus the more rapid turn- Potential explanations include the
~2000 m a over should be accompanied by a possibility that a falling sea level may
(relatively) higher alkalinity and thus result in the precipitation of more seep
carbonate precipitation. This may add carbonate because (i) it increases fluid
5000
to the observed correlation between flow at seeps because of decreasing
deep-water temperature and seep-car- hydraulic pressure on its plumbing
bonate precipitation. Contrarily, Kall- system, (ii) it decreases the thickness
10 000 meyer and Boetius (2004) showed that of the methane hydrate stability zone
0 10 20 30
as-yet-unidentified AOM microbial so that gas hydrates decompose in
Temperature (°C)
consortia in a hydrothermal vent setting deeper sediments thereby increasing
Fig. 5 Stability diagram for gas hydrates
showed highest AOM activities be- seepage, and (iii) it increases the sedi-
(redrawn from Kvenvolden, 1993). Gas tween 35 and 90 C. Clearly, further ment load on the continental slopes,
hydrates are stable in the shaded zone. studies are needed to elucidate the long- thereby increasing lithostatic pressure
(a) Upper depth limit of the hydrate term effect of temperature on AOM- on the methane source rock. A possible
stability zone during the peak of the performing consortia. implication of the first two hypotheses
Cretaceous greenhouse climate. (b) An alternative explanation for the is that seep-carbonate precipitation
Same as (a) but adjusted for a 200 m observed frequency distribution of should be enhanced during times of
higher sea level than presently; note that seep carbonates since the Late Juras- rapidly oscillating sea levels such as
this counters only a minor increase in sic may involve changing sulphate glacial times. This is supported by the
temperature. availability, because AOM is usually coincidence of the extreme increase in

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Terra Nova, Vol 21, No. 4, 279–284 S. Kiel • Linking seep carbonates, sea level and temperature
.............................................................................................................................................................
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Acknowledgements Jensen, P., Aagaard, I., Burke, R.A.J., Peters, S.E. and Foote, M., 2002. Deter-
Thanks to B. Huber, D. Jablonski, Dando, P.R., Jørgensen, N.O., Kuijpers, minants of extinction in the fossil record.
S. Kidwell and J. Peckmann for encourage- A., Laier, T., OÕHara, S.C.M.O. and Nature, 416, 420–424.
ment and stimulating discussion and to the Schmaljohann, R., 1992. ÔBubbling reefsÕ Price, G.D., 1999. The evidence and
five reviewers for their constructive in the Kattegat: submarine landscapes of implications of polar ice during
and insightful criticism. This study was carbonate-cemented rocks support a the Mesozoic. Earth Sci. Rev., 48, 183–
supported by a Walcott fellowship of the diverse ecosystem at methane seeps. 210.
Smithsonian Institution and a Marie-Curie Mar. Ecol. Prog. Ser., 83, 103–112. Price, G.D. and Mutterlose, J., 2004.
Intra-European fellowship by the European Kallmeyer, J. and Boetius, A., 2004. Effects Isotopic signals from late Jurassic-early
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Linking seep carbonates, sea level and temperature • S. Kiel Terra Nova, Vol 21, No. 4, 279–284
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Supporting Information Table S2 Mean values of sea-level supplied by the authors. Any queries
and deep-water temperatures used for (other than missing material) should
Additional Supporting Information
statistic comparison. be directed to the corresponding
may be found in the online version
Please note: Wiley-Blackwell is not author for the article.
of this article:
responsible for the content or func-
Table S1 List of seep-bearing for-
tionality of any supporting materials
mations.

284  2009 Blackwell Publishing Ltd

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