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).
 
 
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.
 
 
Strict anaerobes.
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 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.
Syntrophy between an acetogen and a methanogen
Zinder, 1993
 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.
 CO2 reduction - Slope near 1 Overlap in 13C; separation in D

Fermentation - Slope much

lower
 CO2 reduction - Slope near 1

Methanogenesis in freshwater
systems dominated by acetate
fermentation; in (sulfate-free)
Fermentation - Slope much marine systems, by CO2 reduction
lower
 What controls the 13C of biogenic methane?
(strongly depleted, with a wide range)

N. Blair – link to organic C flux?

-100 -50

Alperin et al., 1992:

120 day sediment incubations
Measure concentrations and rates;
Infer pathways and fractionations
Alperin et al., 1992 120 day sediment incubations

Gas leak

SO4-2 < 0.2 mM

Acetogenesis
Methanogenesis
 Total CH4 production

13C DIC
Increase
due to CO2
reduction

13C CH4
Shifting
Fraction pathways,
from and source
acetate 13C
 13C of CH4 from 13C of CH4
DIC, production (CO2 red.,
 –50 to – 70 acetate ferment.)

13C of CH4 in incubations (instantaneous, and

integrated) reflects variation of pathways, and
substrate 13C
Hoehler et al., 1998 Controls on H2 in anoxic sediments.

7 – 14 day slurry
incubations to estimate
steady-state H2
concentrations. For SR,
methanogenesis, and
acetogenesis, the
observed [H2] levels are
low enough to limit the
next process.
 Greater energy yield (more
negative G) allows sulfate
reducers to outcompete
methanogens for H2.

Zinder, 1993
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

What happens to all this methane?
 
Diffusion (transport) up into oxic zone – aerobic methane oxidation

Bubble ebullition followed by oxidation in atmosphere

shallow seds, with strong temperature or pressure cycles

Anaerobic methane oxidation coupled to sulfate reduction

Gas hydrate formation

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.)
Low T + high P + adequate gas (methane, trace other HC, CO2)
=> gas hydrate formation
 

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
permafrost Continental margin
Known global
occurance of
gas hydrates
 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 (MIS 3)?
(Kennett)
Blair – aerobic methane oxidation in CLB
 What controls the 13C of biogenic methane?
(strongly depleted, with a wide range)

-100 -50

N. Blair – link to organic C flux?

Porewater sulfate and
H2 in Cape Lookout
Bight sediments

Estimated porewater H2 turnover times are very

short (0.1 to 5 s); profile gradients don’t reflect
transport, but “local” production rate variations.
Hoehler et al., 1998
Can imagine a Redfield-type
sulfate reduction stoichiometry:
 
(CH2O)106(NH3)16(H3PO4) + 53SO4-2 =>

106(HCO3-) + 16NH3 + H3PO4 + 53(H2S)

 
Or even just:
 
2(CH2O) + SO4-2 => 2(HCO3-)+ H2S
 

Production of ammonia, H2S, and alkalinity at the depth of SR.

If NH3 and H2S diffuse up and are reoxidized;

consume O2, release H+ close to sediment-water interface
If H2S reacts with Fe++, reduced sulfur and Fe are buried.
But sulfate reducers can only oxidize a limited suite of simple organic
substrates. They typically function as part of a community that
includes fermenters, acetogens, and methanogens, as well as sulfate
reducers.
 
(Fenchel and Finlay, Ecology and Evolution in Anoxic Worlds)
 Jorgensen, 1983

 
The pathways are complex and variable, the processes are tightly linked,
production and consumption of intermediates are rapid and in balance, …
 
Alperin, AMO-SR
Skan Bay AK