Deconstructing the Fantastic Plumes of Methane Recently Observed in the East Siberian Arctic Shelf (ESAS)

Cornell University Earth and Atmospheric Sciences, Snee Hall David Willson, Stanbridge Capital: February 2nd, 2012.

The East Siberian Arctic Shelf (ESAS)

75% o the 2.1 million km2 S e is < 40m deep. of e . o Shelf s 0 90% < 70m deep. Observed CH4 releases from 6-70m.

The Arctic Super Carbon Pool (Shakhova 2009 & 2010)

In the Siberian Arctic Shelf alone, where the six great Siberian rivers deliver their waters, the amount of organic carbon that accumulates annually in the bottom sediments approximately equals that accumulated over the entire open-sea area of the World Ocean. h W ld O ESAS Corg in permafrost ~500 Gt (mostly in the form of peat). 1,000 Gt of C-CH4 in the Methane Hydrate Stability Zone (MHSZ=100m thick) . In methane hydrates, the gas molecules (20% of the volume) are trapped in crystalline cells consisting of water molecules (80 %) held together by hydrogen bonds. Methane in the form of Free Gas beneath the MHSZ is estimated at ~700 Gt C-CH4
This represents 390x worldwide natural gas production (!) so a small leak is a big problem!

The ESAS has not been considered to be a methane source because it was believed not to be conducive to methanogenesis, and the permafrost to be acting as an impermeable lid, preventing CH4 escape through the seabed.

20062009 Methane Concentration in the Upper Troposphere

359hpa.png

Could Arctic ppb be high, despite low anthropogenic emissions, because of large methane seeps? What CH4 flows over the last ten years would be implied?

Increase in Arctic Methane Concentrations

November, 2010 N b November, 2011 N b

How Can the Observed Methane Plumes be Reconciled with Models that Suggest a Thick Permafrost Seal, Thawing Only Over Centuries?
Factors may include: Variable geothermal heat flows, due to deep faults. flows faults High local salinity yields unfrozen permafrost. Geologically recurring Vertical Flow Conduits. Only very limited actual stratigraphic data from boreholes Also: Non-obvious Bubble Gas Exchange issues may understate actual flows? Primarily thermogenic gas origin?
Strongly overpressured due to deep hydrate disassociation? Potential for buoyant upflows ? Disguised due to bubble dispersion, and adsorption by thick sediments, combined with biogenic gas.

A Geoengineering Opportunity?/ The Methanogenic Economy

The Behavior of Methane Hydrates is Difficult to Predict

The upper and lower boundaries define the Methane Hydrate Stability Zone (about 100m thick at ESAS). At depths less than 200 meters, methane hydrates would not normally form. The shallow ESAS hydrates are therefore y relic hydrates, which have avoided disassociation by different means, including ice coating : the presence of small amounts of other natural gases, such as CO2, H2S, and ethane (C2,H6), which increase the stability of the hydrate, shifting the curve to the right. h d hif i h h i h Below a certain depth, geothermal heat flows (especially near faults) will cause hydrates to destabilize. h d d bili

ESAS Stratigraphy : Shakhova (December, 2010)

Q. How much heat flow is required to disassociate (or dissolve?) relic" seabed methane hydrates? (including any recent migrations from Pingo-type forms).

Cryolithozone: the uppermost layer of the earths crust, which is characterized throughout the entire year by a freezing temperature in soils and rocks and the presence of, or possibility of, the existence of underground ice. ice The principal characteristic of the cryolithozone is the temperature interval that includes the freezing point of water (0C).

Dissolved CH4 in the Bottom Water for 2005 (Shakhova, 2010)

The Th spatial pattern of dissolved CH4 in b i l f di l d i bottom waters did not correspond to the d h distribution of Corg in surface sediments. Instead, areas with the highest concentrations of dissolved CH4 correlated with fault zones (shown in black lines).

The Laptev Sea is Underlain by Many Active Faults

Most Faults Extend Down 15-20km to the (Hot) Basement

The Lower Bound of the Permafrost Layer Depends Importantly on the Geothermal Heat Flux Assumed (Romanovskii, 2003)
Data on the geothermal heat flux were used as boundary conditions in the models; Data for the shelf, the values were assumed to be equal to the values typical of analogous geological structures on the continent. For rift zones, these values were increased twofold as compared with undisturbed tectonic blocks . blocks But importantly, the chart below is for coastal lowlands, so Onshore. The chart below is Romanovskii, 2005

Geothermal Heat Flow (mW/m2) for East Siberia

Terrestial Heat Flows in areas of dynamic influence of faults (Lysak, 2002). Extremely high values of heat flow over 60008000 mW/m2 are associated with submarine hydrothermal vents in active fault zones (Golubev et al., 1993). When the geothermal heat rate is increased from 40mW/m2 to 70 Mw/m2, then the g , modeled thickness of the permafrost decreases from 500m to 200m. With a heat rate of 95 mW/m2, might the thickness be close to zero? This threshold is met for 25% of Zones of Active Faults (13/52), and 5 % for Uplifts and Blocks (7/88). Methane Torches currently are emanating only from 0.25% of the hot-spot plume areas (which may be 3-5% of the total ESAS).

The Dmitry Laptov Strait is 60 km Wide (Shakhova, 2010)

Predicted Hydrate Deposits (Soloviev, 2002) from WWFs Arctic Climate Feedbacks
One O may i f th t the l infer that th large gap west of the New Siberian Islands is due to the t f th N Sib i I l d i d t th geothermal heat flows rising from the faults down to the Basement. Presumably all methane hydrates have been converted to Free Gas not just the portion closest to faults (?) (?). The degradation of arctic sub-sea permafrost is already releasing methane from the massive, frozen, undersea carbon pool and more is expected with further warming WWF. warming WWF (?)

Formally Silt with Negative-Temperature Sediments is Permafrost

The C2 Borehole had only 25m of Permafrost Thickness (Rachold, 2005)

Borehole C-2, 12km from the shore: at 64m deep the sed e s we e o e oeC , o e s o e: a 6 e sediments were unfrozen despite subzero (permafrost) temperatures because of 2-3% salinity.

How Might Higher Surface Temperatures Accelerate Methane Releases?

Thawing Thick Permafrost: Dmitrenkos model indicates a slow process (1m in 25 years) g f p ( y ) due to insulation from the water column, 30m of thawed sediments, and high ice latent heat . Disassociation of Relic Seabed Methane Hydrates: calculations needed. Ejection or Preferential Melting of vertical Wedge Ice or Pingo Core: Champagne cork analogy, due to overpressure from underlying disassociated hydrates. Is the ice core only weakly bonded to the permafrost, and hence a site of likely failure from overpressure below. Might sandbox-type experiments be illuminating? Note thawing of the Ice Wedge far below the Active Layer Layer.

Melting Pingo (Ice-Cored Mound) and Polygon Wedge-Ice near Tuktoyaktuk, Northwest Territories, Canada

Bubble Plumes Rising from the Seafloor throughout the Water Column
Bubble plumes (probably dominated by CH4) rising from the seafloor throughout Bubble the water column .. in September, 2008. A. High-resolution seismic image shows gas charged sediments (darker areas within sediments) and gas release from the bottom throughout entire water column; B. Echo sounder image showing bubbles arising within the water column up to subsurface water layer (10-15 m depth).

Pursuant to Bubble Transport Mechanics, < 2% of CH4 Surfaces < 20km

Tilted Fault Blocks with Sediment-Filled Grabens (Gulf of Suez)

The Laptev Sea Grabens may fill w ca bo aceous river-borne and thermoe ap ev G abe s ay with carbonaceous ve bo e a d e o abrasion sediments, capable of adsorbing large quantities of methane. The sediments may be deepest at the junction exactly where methane is most likely to have migrated up from. y g p Just as nitrogen strips methane from ascending bubbles, it should also strip methane from the carbonaceous sediments (a well-know coalbed methane trick). The Desorption effect should be especially strong when storms churn the bottom sediments, triggering large methane releases. A diffusion-controlled process is accelerated by lack of ice cover and by storms.

Olahs Sustainable Methanol Economy: A Methanogenic Variant?

S ce 990 Nobel-Laureate Geo ge O a as bee advoca g Sus a ab e Since 1990 Nobe au ea e George Olah has been advocating a Sustainable Energy paradigm called The Methanol Economy. Methanol is a high energy density liquid fuel that can be used by existing IC engines, and also as a p g , power plant fuel by gas turbines: it can be manufactured p yg from CO2 and hydrogen: CO2 + 3 H2 CH3OH + H2O
In Iceland, geothermal energy is being used to manufacture methanol, as such heat and CO2 are abundant. The hydrogen is sourced from natural gas. When the CO2 is sourced from Air Capture, and the hydrogen from electrolysis of water, the process is entirely sustainable, with supplies of each physically unlimited. But because Air Capture and Electrolysis are both energy intensive and expensive, the fuel i h b f l might be 5x more expensive than gasoline, and methanol can also be toxic. i h li d h l l b i A novel variant is The Methanogenic Economy: it can be initiated quickly with CO2 captured from concentrated sources such as power plants, and blended with methane to make a close gasoline proxy, octane: 25 CH4 + 7 CO2 4 C8H18 + 14 H2O proxy Of special interest are classes of methanogens which are known convert CO2 to methane, in conjunction with fermentative microbes (sewage as a substrate). Cycling: CO2 is captured from power plants, converted to CH4 by methanogens in anaerobic biopiles, and blended with CO2 to manufacture (using geothermal heat?) Octane for power generation and transportation.

A Transformational ESAS Geoengineering Opportunity?

The t Th tone of Blogs and press coverage has been Apocalypse or Not? f Bl d h b A l N ? A different perspective would be that the ESAS seeps may have been large for some years. Reducing this amount would yield Climate benefits, in proportion to th t the proposed 140 tg methane reduction in Shindell, 2012: (450) ppb CH4 d t th d ti i Shi d ll 2012 b CH4. Methane could be captured from deep overpressured reservoirs , and a blend of CO2 and biogenic methane captured from the shallow carbonaceous sediments. The CH4/CO2 blend could be used to manufacture octane, using geothermal heat. In this manner, over a period of time:
Potentially problematic ESAS methane emissions might be preemptively reduced, CO2 concentrations in carbonaceous sediments reduced (increasing CH4 capacity), and A significant amount of liquid fuels manufactured, with octane potentially replacing fossil fuel production elsewhere elsewhere.

A Modular Gas-to-Liquids Facility Converts Captured ESAS Methane and CO2 to Liquid Fuels for Power and Transport
Petrobras is testing ship-GTL units for Stranded Gas situations. Onshore GTL Units could be housed within a Dome or other structure. The Liquid fuels could be barged up the Lena River, then by rail to Beijing. The Backhaul could be liquid CO2, captured from Chinese power plants.

Summary Preliminary Conclusions: Related Research Opportunities?

Due to D t variable geothermal heat flows and salinity, the permafrost is an i bl th l h t fl d li it th f ti imperfect seal, and may be pierced by vertical conduits (Wedge Ice, Pingos). 2. There may be some potential for large upward Salt Diapir-type hydrate flows. 3. The amount of Free Gas (390x world CH4 production ) is more of an issue than methane hydrates (already absent for much of the Laptev Sea). 4. Most of the CH4 plumes are related to faults in or near the Laptev Sea area. 5. The CH4 flows from the deeper waters could be large ( a multiple of 7 tg?). 6. The gross CH4 flow may be higher (portions of which may be oxidized to CO2 in the water, and vented beyond the ESAS). y ) 7. Thermogenic gas (including from coal) may have been underestimated. 8. The abundant seabed carbonaceous sediments may absorb CH4 and CO2. 9. 9 Geoengineering may be favorable due to highly concentrated CH4 sources, sources with captured CH4 and CO2 potentially blended to make liquid fuels. 10. Abundant ESAS geothermal heat might be used to manufacture Liquid Fuels. Any follow-up questions can be emailed to dwillson@stanbridgecapital.com . 1. 1

Appendix

How Can the CH4 Plumes Arise Given the Thick Permafrost Seal?
The Arctic Methane Conundrum is readily resolved by assuming a higher rate of deep geothermal heat flow through this heavily faulted area (e.g. 95mW/m2 for (e g faults instead of 70 mW/m2 for fault blocks): thin levels of permafrost (<50m?) would then be implied, which appear consistent with actual deep borehole data. The depth of permafrost has also been overestimated because (a) sub-zero sub zero sediments do not freeze when waters become sufficiently saline (due to local hydrate formation), and (b) the steep gradient for thawed sediments have been ignored. The location of the largest methane plumes appears coincident with deep-seated deep seated extensional faults, the surface expression of which is the Siberian islands. Such Extensional faults reportedly extend 15-20km or more deep, where temperatures are higher (a gradient of 22 C per km of depth away from tectonic plate boundaries, 22C but 25-30C/km or more in active geothermal areas). Such heat flows would promote methanogenesis within deeper strata adjoining faults, turning the peat potentially into lignite, and release very high rates of au s, u g e pea po e a y o g e, a d e ease ve y g a es o methane during the coalification process. The cited source for Dmitrenkos Model (2011) was Delisle (1998), whose paper explicitly acknowledged the uncertainties with faults and heat flow. Dmitrenko also p y g cited the work of Rachold (2005), who warned The presence of unfrozen and saline permafrost suggests that permafrost may not be as cold or thick as predicted by thermal modeling.

In Delisles 1998 Model, the Basis for Dmitrenkos Model, the Role of Faults is Clearly Acknowledged
The l l t d thi k Th calculated thickness of the gas hydrate stability zone for today of the order f th h d t t bilit f t d f th d of almost 1,000 m argues strongly against massive gas diffusion from below. The great uncertainty in the case of the Laptev Sea is the role of the numerous crustal faults, which usually bound the sedimentary basins. They lf l hi h ll b d h di b i Th serve potentially as perennially open pathways for gas migration. The subsea permafrost is a weaker potential caprock. Its thickness is less than that f th th t of the gas hydrate one. h d t In addition, the development of taliks caused by the thermal effect of large rivers running across the shelf opens potential pathways for gas migration. The potential for open pathways for gas migration is much greater than in the case t ti l f th f i ti i h t th i th of the gas hydrate zone. The above theories were developed on the basis of numerical simulations and need to be checked by field work.Talik formation in times of marine d d t b h k d b fi ld k T lik f ti i ti f i regression is an important and unsolved question. Delisle includes as a reference Solovievs 1987 book, which indicates an unfrozen permafrost thickness of just 3 meters at the Dmitry Laptev Strait. f f t thi k fj t t t th D it L t St it

Rachold (2005) Perspective is One of Concern

Subsea pe maf ost is still poorly understood, mainly due to the lack of direct Subsea permafrost poo ly unde stood, di ect observations. Recent results suggest that ice-bearing continuous permafrost with a thickness of 400-600 m can be expected in the coastal offshore zone (Romanovskii. 2005). p ff ( ) Coring at this location thus provides a test for model results. Considering the model data summarized above, a surprising result is that C2 encountered almost p y f z p f f completely unfrozen sediments below a depth of 64.7 mbsl. These unfrozen sediments contain marine pore water with salinities reaching 30 . At temperatures of -1 to -1.5 C these marine sediments remain unfrozen. This observation raises the question of whether present models hold true for q f p f subsea permafrost thickness and distribution throughout the whole Laptev Sea shelf. The presence of unfrozen and saline permafrost suggests that permafrost may not p f f p f gg p f y be as cold or thick as predicted by thermal modeling. Degradation of subsea permafrost and the consequent destabilization of gas hydrates could significantly if not dramatically increase the flux of methane to the y g y y atmosphere.

The Frozen Permafrost Seal May Not be Always as Thick as Modeled

When higher heat flows characteristic of faults and geothermally active areas (relevant for 3-5% of the ESAS?) are applied, the calculated frozen permafrost thickness for the ESAS may decline in thickness from 500m to less than 50m. Comprehensive actual Laptev Sea data clearly suggests that over 3km from shore the average frozen permafrost thickness declines 33m on average (so 11m/km). The 2005 COAST drilling program drilled one borehole 12km from the Laptev Sea shore, and at 77m depth the permafrost was not frozen (due to high salinity, despite sub-zero annual temperatures). Note the confusing terminology permafrost may not actually be frozen, and may be expected to be unfrozen in saline areas). A borehole drilled in the Dmitry Laptev Strait prior to 1987 indicated a frozen permafrost thickness of just 3m, 45km from the shore. Modeled Results do not appear to be consistent with Laptev Sea borehole data , but may be more accurate for the (less faulted) East Siberian Sea. Unfrozen permafrost does not appear to provide a seal against the upward migration of Free Gas supposedly trapped beneath the permafrost- particularly due to characteristic conduits for vertical flow, such as Taliks, Ice Wedges, and Pingos. Our results suggest that degradation of subsea permafrost in the ESAS currently very likely occurs on a wider scale than was previously thought. (Shakhova, 2010)

Methane Hydrates (Shakhova/WWF, 2009)

Gas h d t G hydrates are compounds in which the gas molecules (20% of the volume) are d i hi h th l l f th l ) trapped in crystalline cells consisting of water molecules (80 %) held together by hydrogen bonds. Gas h d t G hydrates can be stable over a wide range of pressures and temperatures. For b t bl id f dt t F example, a unit volume of methane hydrate at a pressure of 26 atmospheres and 0C contains 164 times that volume of gas; thus, 164 m3 of gas are contained in a hydrate volume of 0.2 m3. 0 2 m3 The dissociation of hydrates in response to increasing temperature is accompanied by a substantial increase in pressure. For methane hydrates that formed at 26 atmospheres and 0 C, it is possible to obtain a pressure increase of as much as 1,600 0C 1 600 atmospheres upon dissociation. Hydrates are found in the Arctic and in deep water. They can occur in the form of small (5-12 cm) nodules, as small lenses, or even as pure layers that can be tens of (5 12 nodules lenses meters thick).

Non-Obvious Bubble Gas Exchange Issues May Materially Understate Actual ESAS Sea Bed Methane Flows?
As a bubble migrates upwards from the sea bed, it acts as a semi-permeable membrane, exchanging gases with the water based on partial pressure differences:
Methane flows out very rapidly, while CO2 and nitrogen flow in (among other gases).

Relative to the Hot Spots of the ESAS, the prolific Santa Barbara Channel Methane Seeps have larger peak and average flows/m2: but still only 1.4% of the seeps aggregate methane mass makes it di tl t the surface. t th k directly to th f Of the 98.6% that stays in the water column, an estimated 60% is oxidized (converted to CO2) by microbes, while 40% surfaces >20km distant from the seeps ( d so eventually enters the atmosphere). F ESAS this is included? (and t ll t th t h ) For ESAS, thi i i l d d? Microbial activity may be lower in the oligotropic ESAS due to lower temperatures, but 1,000x CH4 supersaturation may indicate active communities. In recent years, due to less ESAS ice cover and stronger storms that regularly invert the water column:
The volume of potentially diffusion-controlled seeps from grabens may have increased Th proportion of methane in the water column consumed by microbes may have decreased. The i f h i h l db i b h d d

Could ESAS seabed CH4 emissions be a significant fraction of (Shindells) 140 tg/year? (How much dissolved CH4 migrates beyond the ESAS?).

Deep Listric Faults Extend 20km Down to the (Hot) Basement

An Extensional t t i A E t i l tectonic regime broadly analogous to the Great Basin of the i b dl l t th G t B i f th US West, with its characteristic tilted fault blocks?

Basin and Range Region Physical Geography (Joel Michaelson)

Clockwise: Ice Melt, Deep Faults, Fault Map, Laptev Sea Hydrate Gap

An Ice Core can be a Vertical Conduit for Flow

Pingos a e ice co ed circular hills with a height of 3-70 meters and a gos are ce cored c cu a sw e g o 3 70 e e s a d diameter between 30-1000 meters. Large ones usually have exposed ice at their top: this ice at the core of pingos is thought to accumulate because of cryostatic pressure and artesian groundwater flow.

Pingos Often Occur in Groups

Pingo in Eskerdalen Spitzbergen. Pingos are ice-cored mounds that occur in Eskerdalen, Spitzbergen ice cored permafrost regions. They are imprinted upon the seafloor.

A Salt Diapir is Much Wider than a Pingo (at Dmitry Laptev Strait?) How Extension Triggers Diapirism (Jackson, 1994)

Taliks, Pingos, and Ice Wedges are Conduits for Vertical Flow (Schuur)

Mammoth Tusk Cape Coast 1 2005 Borehole Drilling Program

Borehole C-2, 12km from the shore,: at 64m deep the sediments were unfrozen despite b d it subzero (permafrost) temperatures because of 2-3% salinity. ( f t) t t b f 2 3% li it No further boreholes were drilled to investigate this surprise.

When Methane Hydrates Form, the Remaining Water becomes More Saline because No Salt is in the Hydrates
The L t S f lt Th Laptev Sea faults evidence an extensional t t i setting, similar to Th id t i l tectonic tti i il t The Great Basin of the US, which contains a large Salt Lake: might the ESAS also have contained salt lakes prior to inundation? If so these sediments may have never frozen due to their salinity and they may also have characteristic vertical fractures salinity, on the former lake bottom, which would be conduits for the vertical migration of Free Gas. With 20% lake bottom salinity a temperature of almost -12C would be required: salinity, 12C moreover, any (non-saline) methane hydrate formation would further increase local salinity. Freezing 100% of the sediments may be challenging due to the everincreasing local salinity induced by nearby methane hydrate formation.

Methane Emissions and Sinks Houweling (1999)

The most effective sink of atmospheric methane is the hydroxyl radical in the p y y troposphere to create water vapor and carbon dioxide
Origin Natural Emissions Wetlands (incl. Rice agriculture) Termites Ocean Hydrates Natural Total Anthropogenic Emissions Energy E Landfills Ruminants (Livestock) Waste treatment g Biomass burning Anthropogenic Total Sinks Soils Tropospheric OH (Hydroxyl) Stratospheric loss S h i l Sink Total Emissions + Sinks Imbalance (trend) CH4 Emission Mass (Tg/a) 225 20 15 10 270 110 40 115 25 40 330 -30 -510 -40 40 580 20

The lifespan of methane in the atmosphere was estimated at 9.6 years as of 2001; however, increasing emissions of methane over time reduce the concentration of the hydroxyl radical h d l di l

Dissolved CH4 in the Surface Water for 2005 (Shakhova, 2010)

Plume areas are shown: black square, east of the Lena Delta; red square, Pl h bl k f h L D l d the Dmitry Laptev Strait.

Thermogenic Gas from Thick Coal Strata Could Source Free Gas?
Tundra has been compared to peat. As thick buried sediments are exposed to strong heat flows from faults (and folding?) under the Laptev Sea, they may coalify with large volumes of Free Gas released. That much of the estimated 933 GT of ESAS Free Gas could be thermogenic would have profoundly encouraging implications for GeoEngineering. In the 2011 ESAS Survey, there was a single large Torch only every 250km2.

Worlds Largest Coal Basin = Largest Coalbed Methane Play?

Tundra is similar to peat, and under strong local heat may turn to coal.
Texas Lignite Belt thermal exceptions.

The Laptev Sea abuts the 756 GT Lena Coal basin: coals adsorb CH4. Unlike conventional reservoirs, an increasing production profile is common. To the extent that some of the deep sediments at the ESAS may have coalified near faults, this may be relevant. l t

The ESAS has not been considered to be a methane source because it was believed The not to be conducive to methanogenesis, and the permafrost to be acting as an impermeable lid, preventing CH4 escape through the seabed (Shakhova, 2008)

Solubility of CO2 in Ethanol