Methane hydrates (Clathrates):

New Fuel or Major Threat for

Increased Global Warming, Huge
Slumps and Disastrous
Tsunamis?

Clathrates
(methane hydrates)
What are clathrates?
What is the origin of the methane in
clathrates?
Beasties living off decaying clathrates
Where do clathrates occur naturally?
How much clathrates are there?
Clathrates as possible fuel source
Clathrates as a cause of tsunamis/ climate
change

What are Methane

Hydrates?
Methane Hydrates are one
example of clathrates
Clathrates are compounds which
consist of a cage structure, in
which a gas molecule is trapped
inside a cage of water molecules
Methane (CH4) is trapped in
Water (H2O) forming an ICE

Grey=carbon
Green=hydrogen
in CH4
Red = oxygen
White= hydrogen
in H2O

1 m3 of hydrate -> ~170 m3 methane gas (STP)

Mackenzie Delta of Canadian Arctic

Origin of natural methane

Bacterial degradation of organic matter
in low-oxygen environments within
sediments
Thermal degradation of organic matter,
dominantly in petroleum (e.g., Gulf of
Mexico)

Where do clathrates occur?

How much clathrate is there?
Methane and water must be
available (organic matter:
produced by biota; in oceans:
close to continents)
Clathrate must be stable (ice):
cold and/or high pressure
High latitudes (permafrost)
In medium deep sea sediments (300-2000 m)

Hydrate
Stability

Hydrate
Stability

2013

Gas Hydrate
on the Sea
floor

Beasties!

Organisms living on cold gas seeps

The lair of the ice

worm

Beasties!
Tube
worms
and crab

MODEL OF SEEP CLAM BED

(VAN DOVER, 2000)

SEA WATER

Host
S

Organic material

endosymbiotic chemoautotrophic Archaea

H2S

CO2

sulfate reducing Bacteria

SO 42-

2CH3COOH=CH4+CO2
CH4

2CH2O+SO4= H2S+2HCO3?

coarse,
porous
sediment

How does
the
foodchain in
these seep
communities
function?

How much hydrate is there?

Estimates vary widely: globally 600,000
to 2,000,000 Tcf (trillion cubic feet)
1 Tcf ~ 1 quadrillion Btu (quad) (1015)
World energy use (2000): about 375-400
Quad = 500 Tcf hydrate gas per year
US gas hydrates: estimated at about
100,000 to 600,000 Tcf
Gas hydrates abundant in oil-poor
countries (Japan, India: ~2000 TCM)

Clathrates as fuel:
Problems: how to collect the gas in a controlled way?
Small % recoverable?
Need to be treated as synfuels to
get oil-equivalent
"synthetic fuel" is to describe fuels manufactured via Fischer
Tropsch conversion, methanol to gasoline conversion, or direct
coal liquefaction.

Methane production - Methanogenesis

Substrates / pathways
Isotopic studies
Hydrogen cycling

Methane consumption - Anaerobic methane oxidation

Methane hydrates
(Thermogenic methane)
(Hydrothermal vent methane)

Methanogens (Zinder; Oremland)

Archaea: Single cell
Relatively few species (30-40), but highly diverse
(3 orders, 6 families, 12 genera).

Strict anaerobes.
Highly specialized in terms of food sources
Can only use simple compounds (1 or 2 carbon atoms), and many
species can only use 1 or 2 of these simple compounds.
Therefore, dependent on other organisms for their substrates;
food web / consortium required to utilize sediment organic matter.

Yellowstone : Halobacterias

Two main methanogenic pathways:

CO2 reduction
Acetate fermentation
Both pathways found in both marine and freshwater systems
Many other substrates now recognized

CO2 reduction

Acetate fermentation

Zinder, 1993

Dominant pathway for methanogenesis?

Stable isotope approaches.
4H2 + HCO3- + H+ => CH4 + 3H2O
Distinct D (stable
hydrogen isotope) values
for CO2 reduction and
acetate fermentation, based
on source of the hydrogen
atoms.

All H from water

3 of 4 H from acetate
CH3COO- + H2O => CH4 + HCO3-

Whiticar et al., 1986

CO2 reduction - Slope near 1,

all H from water

Fermentation - Slope
much lower, 1 of 4 H
from water

Whiticar et al., 1986;

but maybe not so simple
see Waldron et al., 1999

Methanogenesis in freshwater
systems dominated by acetate
fermentation (larger
fractionation);
in (sulfate-free) marine systems, by
CO2 reduction (smaller
fractionation)

What happens to all this methane?

Diffusive transport up into oxic zone aerobic methane oxidation
Bubble ebullition (in shallow sediments, with strong temperature or
pressure cycles) followed by oxidation in atmosphere
Anaerobic methane oxidation coupled to sulfate reduction
Gas hydrate formation

Used fluorescent
probes to label, image
aggregates of archaea
(methanogens, red)
and sulfate reducers
(green) in sediments
from Hydrate Ridge
(OR) observed very
tight spatial coupling.

Boetius et al., 2000

Anaerobic methane oxidation coupled with sulfate

reduction
CH4 + 2H2O => CO2 + 4H2

DeLong 2000
(N&V to Boetius et al.)

SO4-2 + 4H2 => S= + 4H20

Known
global
occurance
of gas
hydrates
Most marine gas
hydrates have 13C
values lower than 60
o/oo, and are of
microbial origin.
Hydrates with higher
13C values (> - 40 o/oo)
and containing some
higher MW
hydrocarbons are
thermogenic

Geophysical
signature of gas
hydrates: presence
of a bottom
simulating
reflector in seismic
data, due to velocity
contrast (hydrate /
free gas).
water
sediment
hydrate
free gas

Seismics
The stiffening of the sediments results in increase of the
compressional velocity, Vp and cementation of sediment grains
by hydrate will lead to increase in shear modulus and thereby
shear wave velocity Vs.
This reflector marks the phase boundary
Runs parallel to the sea floor: Bottom simulating reflector
Phase boundary dependent on the thermobaric conditions:
reflector cuts across the dipping sedimentary beds

Left: velocity 'increase' in the

hydrated sediments above the
BSR and 'drop' in free-gas
bearing sediments below,
Right: BSR showing large
amplitude, opposite polarity
seismic event w.r.t seafloor
reflection.
GH

Stable

GH Unstable

Vp=(k+4/3)/
k= Bulk modulus; = Rigidity or Shear
modulus; =density
in hydrate is lower while is
higher than sediment-porewater-gas
system

Pure hydrates have much higher seismic velocity and resistivity compared to
the normal oceanic sediments within the stability zone. So, the presence of gashydrates above the BSR increases the seismic velocity or resistivity.
Whereas, even a small amount of 'free-gas' lying below the hydrated sediments
decreases the velocity considerably

Typical bottom simulating reflector (BSR) over the Blake Ridge in

the Atlantic Ocean and in the KrishnaGodavari basin off the
eastern coast of India

BSR locations on the sediment thickness map in western (left)

and eastern (right) offshore of India

Methane hydrates:
Possibly LARGE fuel source
(natural gas): more than twice all
other fossil fuels
Unknown difficulties in recovery
Production may cause major
slumps, tsunamis, and
exacerbated greenhouse effect

Climate change/Tsunamis
Methane is a strong greenhouse gas
If clathrates are destabilized, huge
amounts of methane are added to the
atmosphere (55 X106 years ago??)
Sediments loose strength==>slip
downslope==> slumps==> tsunamis
Methane is rapidly oxidized to CO2,
also a greenhouse gas

Have clathrates ever been

destabilized in the past?
Increase in temperature, decrease in
pressure (drop sea level)
At the end of the last ice age, megaslumps occurred in regions with gas
hydrates

Warming to LPTM
Late Paleocene
thermal maximum

Abrupt, global low-13C event in late Paleocene

(benthic foraminifera, planktic foraminifera,
terrestrial fossils): A gas hydrate release?

Dickens et al., 1997

High-resolution sampling
of the 13C event.
Magnitude, time-scales,
consistent with sudden
release of 1.1 x 1018 g CH4
with 13C of 60 o/oo, and
subsequent oxidation.
Did warming going into
LPTM drive hydrate
dissociation, and methane
release?
Did similar (smaller)
events occur during the last
glaciation? (Kennett)