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.
 
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.
 
 
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
Acetate fermentation
CO2 reduction
Obligate syntrophy between an acetogen and a methanogen is common

Each species (e.g., a methanogen and an acetogen) requires the other:

the acetogen provides the hydrogen; the methanogen prevents a build-
up of hydrogen (which inhibits the acetogens)
Zinder, 1993
Obligate syntrophy is common
 
Both species (e.g., a methanogen and an acetogen) require the other:
the acetogen provides the hydrogen; the methanogen prevents a build-up
of hydrogen (which inhibits the acetogens)
 
 
In marine sediments, methanogens are competitive only after sulfate
is gone (< 0.2 mM sulfate). Sulfate reducers keep H2 partial pressure
too low for methanogens. (T. Hoehler et al.)
Porewater sulfate and
H2 in Cape Lookout
Bight sediments

Estimated porewater H2
turnover times are very
short (0.1 to 5 s);
profile H2 gradients
don’t reflect transport,
but “local” production
rate variations.

Hoehler et al., 1998

 Hoehler et al. – Microbial communities maintain porewater H 2
concentrations at a minimum useful level (based on the energy
they require to form ATP from ADP). The bulk H2 may reflect
the geometry of the H2 producer / H2 consumer association.

H2 consumer –
sulfate reducer

H2 producer –
fermenter

Higher bulk H2 Lower bulk H2

 Dominant pathway for methanogenesis?
Stable isotope approaches.

4H2 + HCO3- + H+ => CH4 + 3H2O

All H from water Distinct D (stable

hydrogen isotope) values
for CO2 reduction and
acetate fermentation, based
on source of the hydrogen
atoms.

3 of 4 H from acetate

CH3COO- + H2O => CH4 + HCO3-

Whiticar et al., 1986

 Whiticar et al., 1986;
CO2 reduction - Slope near 1, but maybe not so simple
all H from water see Waldron et al., 1999

Methanogenesis in freshwater
systems dominated by acetate
fermentation (larger fractionation);
Fermentation - Slope much
in (sulfate-free) marine systems, by
lower, 1 of 4 H from water
CO2 reduction (smaller fractionation)
What happens to all this methane?
 
Diffusive transport up into oxic zone – aerobic methane oxidation

Bubble ebullition (in shallow seds, with strong temperature or

pressure cycles) followed by oxidation in atmosphere

Anaerobic methane oxidation coupled to sulfate reduction

Gas hydrate formation

 Alperin and Reeburgh, 1984

Skan Bay, AK.

Seasonally anoxic bottom
water, sediments uniformly
black, with millimolar
hydrogen sulfide in p.w..
Oxygen penetration depth = 0

Anaerobic methane oxidation “controversial” (impossible)

– no AMO mechanism had been demonstrated,
no organism capable of AMO had ever been isolated.
Alperin and Reeburgh, 1984

C based CH4 oxidation rate profile

14

consistent with pore water methane profile;

methane oxidation to CO2 in anoxic zone.
Stable isotope profiles also consistent with
methane oxidation to CO2 in anoxic zone.
Alperin and Reeburgh, 1985 Sulfate profiles and SR rate profiles match,
too.
Anaerobic methane oxidation by a consortium, made up of:
 
sulfate reducers (with H2 as electron acceptor)
SO4-2 + 4H2 => S= + 4H20
 
And
 
methanogens (running in reverse, due to low pH2)
CH4 + 2H2O => CO2 + 4H2

Together yielding

CH4 + SO4-2 => HS- + HCO3- + H2O

(Hoehler et al., ‘94)

 
 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

H2S production

CH4 consumption

Sediment
incubations (Hydrate
Ridge)
demonstrating
anaerobic methane
oxidation, strong
response to CH4
addition.

Nauhaus et al., 2002

 Anaerobic methane oxidation coupled with sulfate reduction

CH4 + 2H2O => CO2 + 4H2

DeLong 2000 SO4-2 + 4H2 => S= + 4H20

(N&V to Boetius et al.)
 Another fate for methane – gas hydrate formation

Low T + high P + adequate gas (methane, trace other HC, CO2)

=> gas hydrate
 

Why do we care about methane hydrates?

 
Resource potential
Fluid flow on margins
Slope destabilization / slope failure
Chemosynthetic biological communities
Climate impact potential
 Kvenvolden, ‘88

1 m3 hydrate => 184 m3 gas + 0.8 m3 water

DIC = 980
Terr bio = 830
Peat = 500
Atm = 3.5
Mar bio = 3
Total fossil fuel = total hydrate =
5000 x 1015 gC 10,000 x 1015
gC (a guess!)
 Methane
hydrate stability

Methane gas

Methane hydrate
 Stable T and P, not
enough methane

permafrost Continental margin

 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
 Porewater evidence of hydrate dissociation:
low Cl- in zone of hydrate dissociation
(during core recovery; decompression, warming)
Warming to LPTM – Abrupt, global low-13C event in late Paleocene
Late Paleocene (benthic foraminifera, planktic foraminifera,
thermal maximum 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)
 Simultaneous low-13C
excursions in benthic and
planktonic foraminifera
consistent with release (and
oxidation) of light methane,
as a result of destabilization
of clathrates – the .
 Marine clathrates

Terrestrial wetlands
A constraint on hydrate release from
the D of methane in ice cores.

Sowers, 2006
 Clathrate release
should result in lower
D values (black
model line); instead,
D tends to increase
with CH4 increase.
Sower’s conclusion -
the glacial methane
increases were not
caused by clathrate
release.

Sowers, 2006