Hydrocarbons in the Deep Earth?

[Chromium6]

Improving exposure assessment of complex hydrocarbon mixtures in the aquatic environment

http://igitur-archive.library.uu.nl/dis ... /muijs.pdf

Contents

Introduction

Temperature-dependent Bioaccumulation of Polycyclic Aromatic
Hydrocarbons

Evaluation of clean-up agents for total petroleum hydrocarbon analysis in
biota and sediments

A closer look at bioaccumulation of petroleum hydrocarbon mixtures in
aquatic worms

Assessing the bioavailability of complex petroleum hydrocarbon mixtures
in sediment

Testing the potential of passive samplers to assess actual in situ
bioaccumulation of PAHs and petroleum hydrocarbon mixtures

[Chromium6]

Methane Production from Gas Hydrate Deposits through Injection of Supercritical CO2

Christian Deusner *, Nikolaus Bigalke, Elke Kossel and Matthias Haeckel *
GEOMAR, Helmholtz Centre for Ocean Research Kiel, Wischhofstr.1-3, D-24148, Kiel, Germany;
E-Mails: nbigalke@geomar.de (N.B.); ekossel@geomar.de (E.K.)
* Authors to whom correspondence should be addressed; E-Mails: cdeusner@geomar.de (C.D.);
mhaeckel@geomar.de (M.H.); Tel.: +49-431-600-1415; Fax: +49-431-600-1400.
Received: 5 April 2012; in revised form: 5 May 2012 / Accepted: 7 June 2012 /
Published: 25 June 2012

Abstract: The recovery of natural gas from CH4-hydrate deposits in sub-marine and
sub-permafrost environments through injection of CO2 is considered a suitable strategy
towards emission-neutral energy production. This study shows that the injection of hot,
supercritical CO2 is particularly promising. The addition of heat triggers the dissociation of
CH4-hydrate while the CO2, once thermally equilibrated, reacts with the pore water and is
retained in the reservoir as immobile CO2-hydrate. Furthermore, optimal reservoir
conditions of pressure and temperature are constrained. Experiments were conducted in a
high-pressure flow-through reactor at different sediment temperatures (2 °C, 8 °C, 10 °C)
and hydrostatic pressures (8 MPa, 13 MPa). The efficiency of both, CH4 production and
CO2 retention is best at 8 °C, 13 MPa. Here, both CO2- and CH4-hydrate as well as mixed
hydrates can form. At 2 °C, the production process was less effective due to congestion of
transport pathways through the sediment by rapidly forming CO2-hydrate. In contrast, at
10 °C CH4 production suffered from local increases in permeability and fast breakthrough
of the injection fluid, thereby confining the accessibility to the CH4 pool to only the most
prominent fluid channels. Mass and volume balancing of the collected gas and fluid stream
identified gas mobilization as equally important process parameter in addition to the rates
of methane hydrate dissociation and hydrate conversion. Thus, the combination of heat
supply and CO2 injection in one supercritical phase helps to overcome the mass transfer
limitations usually observed in experiments with cold liquid or gaseous CO2.


1. Introduction

Large amounts of natural gas, predominantly methane, are stored in gas hydrates in sediments
below the seafloor and the permafrost [1]. Current estimates of the global methane hydrate inventory
range between 1000 and 10,000 Gt of carbon [2–5]. Motivated by these results, gas hydrate research
activities worldwide center around the exploitation of this potential new energy resource. The methods
that are currently discussed to produce the methane from gas hydrates are generally derived from
standard techniques used in conventional oil and gas business, i.e., reduction of the pressure in the
reservoir and thermal stimulation, as well as injection of hydrate inhibitors, such as salt, to induce
dissociation of the gas hydrates [6]. In addition, the substitution of CH4 by CO2 as guest molecule in
the gas hydrate structure has been proposed as a more elegant production technology with respect to
greenhouse gas policies [7,8].

All of these methods have been studied in laboratory experiments to validate their feasibility as well
as in numerical simulations to gain first ideas about their applicability on reservoir scale. First
production tests were carried out in the permafrost reservoir of Mallik in northern Canada in 2002 [9]
as well as in 2008 [10]. Gas hydrates were successfully destabilized by injection of hot water and by
depressurization, respectively, producing limited amounts of CH4 gas over a few days. Further field
trials in 2012 will test the chemical exchange of methane in gas hydrates by injection of CO2 below the
permafrost of the Alaska North Slope [11] and the depressurization technique in the first offshore test
in the Nankai Trough [12,13].

Overall, the conclusions drawn from those studies are that thermal stimulation by injecting hot
water is slow and inefficient, whereas depressurization seems to be the more promising strategy [6].
However, due to the endothermic nature of gas hydrate dissociation, in the long run, the reservoir will
cool down, re-establishing stable conditions for gas hydrates and consequently, methane production
rates are expected to cease after some time [14,15].

Thus, being able to achieve stable and economic methane production rates will require a
combination of depressurization and methods (re)activating the methane hydrate reservoir.
One elegant way to activate the methane hydrate reservoir is the injection of CO2. Since CO2
hydrate is thermodynamically more stable than CH4-hydrate and both form structure-I, the exchange
reaction will proceed exothermically [16], adding heat to the system. Besides its attractiveness in
combining energy production with CO2 storage as a measure to mitigate further increases in
greenhouse gas emissions to the atmosphere, a technological advantage is that it sustains the integrity
and geo-mechanical stability of the sediments, thus reducing the potential risk of slope failures.
Several laboratory-based studies have shown the feasibility of the hydrate conversion reaction on
pure or sediment-dispersed gas hydrates and from molecular scale to volumes of a few liters (an
overview is given in Discussion). However, the overall reaction rate turns out to be quite sluggish and
the conversion is often incomplete. This results primarily from a shell of CO2-hydrate that forms
around the methane hydrate grain. Any further mass transport of CO2 into and CH4 out of the inner
core is drastically slowed down or even completely inhibited as analogous experiments with C2
H6 as attacking guest molecules have shown [17]. Moreover, excess water, as usually encountered in the
pore space of hydrate deposits, generally induces immediate CO2-hydrate formation blocking
permeable pathways for the gas exchange.

http://www.mdpi.com/1996-1073/5/7/2112/pdf


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Scientists probe atomic structure and dynamics of water under deep Earth extreme pressure and temperature conditions


08-03-2013

Water is one of the most studied materials on Earth and has been the focus of dedicated research for decades. Despite it being a very simple compound of two common elements, two hydrogen atoms and one oxygen atom, researchers still struggle to describe the unusual structure and dynamics of liquid water. Now, a team of scientists have used synchrotron radiation to reveal the microscopic structure of water under conditions of extreme pressure and temperature. The results were published on 11th March 2013 in the Proceedings of the National Academy of Sciences of the USA (PNAS).


http://www.esrf.eu/files/live/sites/www/files/news/general/water-gas/index_html/image.jpg

Liquid water seen through an optical microscope during the experiment plus, on the right, a schematic sketch based on simulations of the molecular dynamics of liquid water. Image courtesy C. Sahle

When subject to extreme temperature and pressure, water exists in the so called super-critical state and exhibits a number of peculiar characteristics very different to those of the water that flows through our taps. In these extreme conditions, water becomes a very aggressive solvent, catalysing otherwise impossible chemical reactions like, for example, the oxidation of hazardous waste or the conversion of sewage into clean water and gases like hydrogen, methane, carbon dioxide and carbon monoxide.

Extremely high temperature and high pressure conditions can be found in the lower crust and upper mantle of the Earth. Here, the unique properties of super-critical water are believed to play a key role in the transfer of mass and heat as well as in the formation of ore deposits and volcanoes. Super-critical water is even thought to have contributed to the origin of life. Insight into the structural properties of water on an atomic scale are essential to understanding the role of liquid water in these processes.

The team of scientists from the Technische Universität Dortmund (Germany), the University of Helsinki (Finland), the Deutsches GeoForschungsZentrum in Potsdam, (Germany), and the European Synchrotron Radiation Facility (France), used X-ray spectroscopy on the ESRF's ID16 beamline to study the structural properties of water in the super-critical state.

The challenge that faced the research team was to study liquids and gases under extreme conditions of high temperature and high pressure. The high performance of ID16 in terms of high flux, energy resolution and highly focused beam was essential to the success of this unprecedented study.

Although conventional spectroscopic analysis techniques can provide key insights into the atomic structure of a substance, they are not well suited to studying water under super-critical conditions because of the complex environment needed to maintain water in this state.

The research exploited the ESRF's hard X-rays to access the oxygen K-edge in a complex environment finding that water evolves systematically from liquid-like to more gas-like at high temperatures and pressures.

Based on the close resemblance between the theoretical and measured data, the team was able to extract detailed information about the atomic structure and hydrogen bonding of water. They showed that according to the theoretical model, the microscopic structure of water remains spatially homogeneous throughout the range of examined temperatures and pressures.

"The unparalleled results obtained here are a good example of new possibilities open to the scientific community for experiments impossible to conduct with other techniques," says Laura Simonelli, scientist on ID20. "Recently, ID16 was upgraded and moved to ID20 where the beamline has been vastly improved in terms of intensity, beam focus, stability and energy resolution. The astounding new X-ray Raman spectrometer will give access to a novel signal to noise ratio with a very wide covering of solid angles."

Publication

Microscopic structure of water at elevated pressures and temperatures, C.J. Sahle, C. Sternemann, C. Schmidt, S. Lehtolab, S. Jahn, L. Simonelli, S. Huotari, M. Hakala, T. Pylkkänen, A. Nyrow, K. Mende, M. Tolan, K. Hämäläinen, M. Wilke, PNAS (2013);

dx.doi.org/10.1073

http://www.esrf.eu/news/general/water-gas/index_html

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Wednesday, June 25, 2008
Geological Society of Nevada presentation - March 21, 2008
THE SERPENTOSPHERE
submitted February 20, 2008

Stanley Keith 1, Monte Swan 1, Martin Hovland 2, Håkon Rueslåtten 3, Hans Konrad Johnsen 2 and Norman Page 4

1 MagmaChem Exploration, Inc, PO Box 950, Sonoita, AZ 85637
2 Statoil Hydro, Forusbeen 50, N-4035 Stavenger, NORWAY
3 Numerical Rocks, Stiklestadveien 1, N-7041, Trondheim, NORWAY
4 2649 N. Martin Ave, Tucson, AZ 85719

The Serpentosphere consists of an earth-wide nearly continuous layer (or spherical shell) of rock dominated by serpentine group minerals (serpentinite). The Serpentosphere is typically about two kilometers thick beneath ocean basins where it is mainly composed of lizardite. Beneath continents, the Serpentosphere is mainly composed of antigorite (alpine peridotite/serpentinite) and may be several kilometers thick. The base of the Serpentosphere coincides with the gravity and high-velocity seismically defined transition beneath both continents and ocean basins commonly referred to as the Moho. Beneath ocean basins and adjacent to spreading centers, oceanic Serpentosphere is continuously generated by the interactions of deep circulating marine composition water – partly in super-critical state – with harzburgitic peridotite in a process referred to as serpentinization. Conversion of the harzburgite to lizarditic serpentine under supercritical condition is texturally preservative and probably induces about 40% volume expansion. The volume expansion provides an excellent mechanism to expel and propel fluid products – including hydrocarbons – from the area of serpentinization to seep sites at the crust hydrosphere/atmosphere interface. A downward diffusing, super-critical serpentinization front is present beneath every ocean basin and is more active where it originally formed near oceanic ridge thermal anomalies. When oceanic Serpentosphere is subducted beneath continental or oceanic crust areas, it converts to antigorite-dominated serpentinite rock (generally coincident with greenschist facies metamorphism). During flat subduction, the relatively low-density antigorite ‘floats’ and is underplated to the base of the continental crust at the Moho geophysical interface.

In effect, both oceanic and continental Serpentospheres reflect a deep ‘weathering’ process that consists of the interaction of deep crustal and oceanic, water-dominated fluids with the upper portion of a mainly harzburgitic peridotite at the top of the earth’s lithospheric mantle. The process is analogous to the formation of the pedosphere through interactions of the earth’s hydrosphere-atmosphere layer with the top of the earth’s lithospheric crustal layer. In this context, the Serpentosphere may be viewed as a thin membrane that separates water-poor, life-free abiogenetic processes in the mantle from water-rich, life-related processes above the Serpentosphere in the oceanic crust.

The Serpentosphere has enormous and novel implications for four major geologic problems that are of current interest to the geologic and social community: the driving mechanism for plate tectonics, the origin of life, the origin of hydrocarbons, and contributions to global climate. A close relationship between trace elements in crude oils and serpentinite has been found. Migration of the serpentine-associated hydrocarbons to seep sites on the ocean floor and in subaqueous continental environments is essentially the base of the food chain for the biosphere and provides a nutrient and energy source for life in these environments. Heat, methane and carbon dioxide generated during the serpentinization reaction provide a major thermal and greenhouse effect to the earth’s hydrosphere-atmosphere system that is overlooked and underappreciated by the current global climate science. The ductility of the serpentine group minerals provides the tectonic "grease" that allows crustal plates to be able to slide and glide around on the earth’s crust at the Serpentosphere/Moho interface. Because Serpentosphere has been continuously generated since the beginning of geologic time it must be considered as one of the fundamental entities of our water-surfaced planet – the only water-planet we know of…

http://www.serpentosphere.blogspot.com/ ... evada.html

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Bacteria ate up all the methane that spilled from the Deepwater Horizon well

By Ed Yong | January 6, 2011 3:00 pm
On April 20, 2010, a bubble of methane raced up the drill column of the Deepwater Horizon oil rig, bursting through the seals and barriers in its way. By the time it exploded on the platform’s surface, it had grown to 164 times its original size. The rig, severed by the explosion, caught fire and sank two days later, allowing oil and gas to spew into the Gulf of Mexico for 83 long days.

This chaotic methane bubble was just a vanguard. With the well unsealed, substantial amounts of the gas were released into the gulf. This plume of dissolved methane should have lurked in the water for years, hanging around like a massive planetary fart. But by August, it had disappeared. On three separate trips through the gulf, John Kessler from Texas A&M University couldn’t find any traces of the gas above background levels. He thinks he knows why – the methane was eaten by bacteria.

The gas pouring out of the broken well spurred the growth of bacteria called methanotrophs, which can break down methane as their only source of energy. They made short work of the gas. By the time that Kessler reached the gulf, just four months after the initial blowout, he found plenty of bacteria and precious little methane.

“Kessler’s paper is very nice work,” says Terry Hazen, who has studied how bacteria reacted to the Deepwater Horizon disaster. “I also suspected that methanotrophs would be active very quickly with this release of methane. We also have supporting data that we have not yet published… wish we had gotten ours out faster.“

Kessler’s discovery goes beyond last year’s disaster. It also tells us about what happens to methane bubbles that naturally rise from the deep ocean, all over the world. Within the ocean floor, methane lies trapped within cages of ice called methane clathrates (or methane hydrates). Methane naturally escapes from these deposits, as well as from undersea vents and natural oil or gas seeps. If the gas reaches the atmosphere, it could have serious effects on the planet’s climate. After all, methane is a potent greenhouse gas and undersea clathrates contain about twice as much carbon as all the fossil fuels in the world.

But first, the gas has to reach the atmosphere, and Kessler thinks that this is unlikely. While scientists can hardly release large bursts of methane to see what happens, they can rely on “natural experiments” like the unplanned surge that followed the Deepwater Horizon well. If that gas failed to make it past the gauntlet of underwater bacteria, then natural seeps would probably meet the same fate.

Some scientists have suggested that methane freed from clathrates could have contributed to the climate upheavals behind some of Earth’s greatest extinctions events, including the day when life nearly died – the Permian-Triassic extinction. *

Greg Retallack from the University of Oregon initially backed this idea, but his mind has since changed. “I love this paper as it signals the final break with my long love affair with methane clathrate release as a cause of [the Permian-Triassic] mass extinction,” he says. “It seems that marine methane cannot even make it out of the ocean because it’s rapidly consumed there.” **

Richard Camilli, who has studied the Deepwater Horizon oil plume, agrees. He says that Kessler’s conclusions probably apply to natural methane leakages, as well as to other oil spills too. “[It] is likely to become a classic reference,” he says.

In June, when David Valentine first described the plume of oil in the Gulf, he found that most of the methane was hanging in a layer between 800 and 1200 metres down. When Kessler arrived at the same area in late August, aboard the NOAA Ship Pisces, he found no traces of it. He did, however, find the degraded remnants of oil chemical and a suspiciously low amount of oxygen.

Many methane-eating bacteria use up oxygen to break down the gas, so Kessler reasoned that the microbes had done away with the methane. He even found the bacteria in question. In September, Kessler recovered several species of methane-eating bacteria from seven different sites. In some areas, these specialists made up a third of the local bacteria.

Back in June, the methane-eaters were nowhere to be found. Instead, Valentine and Hazen detected several other groups of bacteria that were breaking down other oil hydrocarbons, such as ethane and propane. They were first on the scene. Valentine predicted that other species would follow and mop up the methane, in “boom and bust cycles of bacterial succession”. He was right. By September, the bacteria that dominated the gulf in June had all but vanished and the methane-eaters had taken their place. Even they were no longer active – they were just the remnants of a population that had bloomed in July and August.

Hazen adds that the methane-eaters “have the ability to degrade over 300 other compounds,” and may have helped the clean-up efforts in the Gulf, beyond just breaking down the methane. He has been working on ways of turning this bacterial appetite to our advantage. In 1995, Hazen patented a process for seeding polluted groundwater with methane, to stimulate the growth of bacteria that would break down the other contaminants. Many companies around the world now use this process, enticing bacterial janitors with a methane menu.

Footnotes

* This scenario was the basis of one of the worst pieces about the Deepwater Horizon disaster – a frenzied article claiming that BP’s drilling operation “may have triggered an irreversible, cascading geological Apocalypse that will culminate with the first mass extinction of life on Earth in many millions of years.” It was ably debunked.

** It’s possible that the Permian-Triassic event might have involved methane in such large amounts that it “would have overwhelmed the methanotrophs capable of handling the small Gulf spill.” But Retallack can’t find enough methane clathrates in the ocean to account for such a large plume. He still thinks that methane was still involved in the Permian extinction but now he suspects it came from disturbed coal seams.

Reference: Science http://dx.doi.org/10.1126/science.1199697
http://blogs.discovermagazine.com/notro ... pGXAW2PUqh

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ABIOGENIC ORIGINS

Multiple abiogenic processes have been proposed for the formation and accumulation of oil and gas. The two most commonly cited processes proposed are (1) the degassing of the mantle and the polymerization of low-molecular-weight hydrocarbons and (2) the serpentization of ultramafic rocks combined with a Fischer-Tropsch reaction. Both processes were discussed during this conference as well as some other possible mechanisms.

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Keith and Swan reported an association between the hydrothermal processes that form metallic ore deposits and petroleum occurrences. The authors concluded that this relationship suggests that the petroleum forms as part of a hydrothermal reaction sequence. They noted that these hydrothermal hydrocarbons form at temperatures well above the oil window. Keith and Swan proposed a four-stage process. The first stage is serpentization, which through a series of reactions (e.g., Fischer-Tropsch in the presence of iron-nickel and cobalt catalysts) produces a hydrocarbon-bearing fluid. The second stage is the vertical migration of hydrocarbon-bearing hydrothermal solutions. They suggested that the conduit for this fluid movement is commonly strike-slip faults. The third stage is associated with the hydrothermal diagenesis of reservoirs including the formation of high-temperature (saddle) dolomites. The authors suggested that such fields like Ghawar in Saudi Arabia are possible examples of such hydrothermal deposits. The authors further noted that the dolomitization process itself can be an effective means for creating hydrogen and methane. Keith and Swan stated that several large methane-charged hydrothermal seeps have been identified in transform settings such as Lost City (on the Mid-Atlantic Ridge). The fourth stage is the seepage of these fluids and the formation of metalliferous black shales, either nonuraniferous black shales derived from magnesian dunitic peridotite or uraniferous black shales derived from alkalic spinel lherzolite peridotite. They infer that the black shales are a remnant of hydrocarbon seepage instead of a hydrocarbon source and that the associated hydrocarbon seeps provide an energy and nutrient source that sustains the biosphere. Also, they produced evidence that virtually all oils contain diamondoid compounds, which are temperature and pressure resistant.

Charlou, Donval, Jean-Baptiste, Levache, Fouquet, Foucher, and Cochonat also discussed the abiogenic production of petroleum through serpentization of ultramafic material. The driving mechanism is fluid circulation, represented by hydrothermal vents associated with slow-spreading midocean ridges. To support this model, marine geology cruises that examined the Mid-Atlantic Ridge were reviewed. Charlou et al. noted the presence
of several high hydrogen and methane discharge areas including Rainbow.

Most of this methane was derived through serpentization of ultramafic rocks producing hydrogen, which in turn reacts with CO or CO2 in a Fischer-Tropsch-type reaction to yield hydrocarbons. The methane produced in this manner is isotopically heavy. In addition to methane, the authors reported the presence of a much larger suite of organic compounds, including alkanes, alkenes,alcohols, aldehydes, ketones, esters, and a collection of cyclic hydrocarbons. At the Rainbow location, compounds with at least 29 carbons have been reported.

Charlou et al. proposed that minerals such as pyrite, chalcopyrite, and sphalerite act as catalysts for the formation of these higher molecular weight hydrocarbons. They further noted that the degree of polymerization increases with increasing pressure. It was reported that several experimental studies have produced similar organic materials under hydrothermal conditions. The authors identified several key questions, including where the organic compounds are synthesized within the ultramafic plumbing system and what the best conditions are for the formation of these organic molecules. The authors concluded that additional data obtained on both fluid and rock samples on and off the ridge axis will be required to obtain the answers to these questions.

Szatmari, Da Fonseca, and Miekeley suggested that, in addition to an organic (or biogenic) origin, a second inorganic origin cannot be excluded for some oil accumulations. The authors suggest that several lines of evidence that can be used to support an inorganic origin exist. For example, they suggested that the Schulz-Flory distribution of n-alkanes, where the log of alkane abundance is linearly related to the carbon number observed on a synthetic petroleum formed through Fischer-Tropsch, and a suite of naturally occurring Brazilian oils are both indicators of polymerization (and not a result of thermal cracking). The authors also report that the trace element composition of oils better matches that of chondrites, serpentinized peridotites, and primitive mantle material when compared with oceanic or continental crust, with no correlation observed with seawater. Observed variability in trace element compositions may be a reflection of the mixing of different sources. They further suggested that the relative abundance of saturated and unsaturated aliphatics indicates a high hydrogen partial pressure within the setting in which they formed. Szatmari et al. suggested that this hydrogen formed through hydrothermal serpentinization of peridotites. This hydrogen would, in turn, participate in a Fischer-Tropsch reaction catalyzed by trace elements present in the peridotites to form oil. The authors further reported that deformation and unroofing associated with rifting and continental breakup provide a mechanism for this oil to migrate vertically into shallow traps.

http://geoclasses.tamu.edu/gandg/mancin ... s/Katz.pdf

[Chromium6]

Large Release Of Methane Off Los Angeles Coast — Unusual concentrations detected by haz-mat crews

Chris Carrington
The Daily Sheeple
March 7th, 2013

Typical methane bubbles

Reports of a foul smell in the Santa Monica area caused dozens of calls to the local fire department. Brian Humphrey, spokesman for the department said:

“This morning there was a large release of natural ocean floor methane released in the Santa Monica Bay. This methane is not toxic and disperses easily.”

Methane, which is 23 times more potent as a greenhouse gas than carbon dioxide and is highly flammable is stored in massive quantities in sea beds around the world. The oceanic form, methane clathrate, sometimes called hydromethane is stable until its disturbed. Disturbance can occur from raised ocean temperatures or oceanic earthquakes, which are often caused by techtonic plate movement and though human interference such as pipeline laying can also cause the release of the gas.

Once released the methane bubbles to the surface, releasing sulphurous gasses as the bubble ‘pop’ on the surface.

http://www.thedailysheeple.com/large-re ... ews_032013

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Wednesday, March 21, 2012

Methane Hydrate

Also known as hydromethane, methane ice, gas hydrate, and methane clathrate.

A large amount of methane that trapped within a crystal structure of water, forming a solid similiar to ice and formed a solid clathrate compound (clathrate hydrate).

Found under sediments on the ocean floors. Carbon that bound in gas hydrates is estimated to total twice the amount of carbon to be all known fossil fuels on earth.

Methane hydrates are believed to form by migration of gas from dept along geological faults, followed by precipitation, or crystallization on contact of the rising gas stream with cold sea water Methane clathrates are also present in deep Antartic ice cores, and record a history of athmospheric methane concentrations, dating to 800,000 years ago. The ice-core methane clathrate record is a primary source of data for global warming research, along with oxygen and carbon dioxide.

Structure

The average methane clathrate hydrate composition is 1 mole of methane for every 5.75 moles of water, though this is dependent on how many methane molecules "fit" into the various cage structures of the water lattice. The observed density is around 0.9 g/cm3. One litre of methane clathrate solid would therefore contain, on average, 168 litres of methane gas (at STP).

Methane forms a structure I hydrate with two dodecahedral (12 vertices, thus 12 water molecules) and six tetradecahedral (14 water molecules) water cages per unit cell. This compares with a hydration number of 20 for methane in aqueous solution. A methane clathrate MAS NMR spectrum recorded at 275 K and 3.1 MPa shows a peak for each cage type and a separate peak for gas phase methane. Recently, a clay-methane hydrate intercalate was synthesized in which a methane hydrate complex was introduced at the interlayer of a sodium-rich montmorillonite clay. The upper temperature stability of this phase is similar to that of structure I hydrate.







http://greycrescent.blogspot.de/2012/03 ... e-ice.html

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Active Volcano Found Under Antarctic Ice: Eruption Could Raise Sea Levels
Inevitable eruption will speed up ice loss on frozen continent, study says.

Ker Than for National Geographic

Published November 18, 2013

A newly discovered volcano found buried beneath a thick layer of ice in Antarctica could speed up ice loss and raise global sea levels when it erupts, scientists say.

The finding, detailed in the current issue of Nature Geoscience, marks the first time that an active volcano has been discovered under the ice of the frozen continent. (Also see "Giant Undersea Volcanoes Found Off Antarctica.") http://news.nationalgeographic.com/news/2011/07/110715-undersea-volcanoes-antarctica-science-tsunamis/

When it erupts—which no one can predict—the volcano "will create millions of gallons of water beneath the ice—many lakes full," study leader Doug Wiens, professor of earth and planetary science at Washington University in St. Louis, said in a statement.

This water will rush beneath the ice toward the sea and feed into one of the major ice streams that drain ice from Antarctica into the Ross Ice Shelf, Wiens explained.

What's new?

The new volcano's discovery was accidental. In January 2010, scientists set up a series of seismometers, or earthquake detectors, on Marie Byrd Land, a highland region of West Antarctica.

The instruments array detected two swarms of earthquakes about one year apart, in 2010 and 2011. The earthquakes were small, with magnitudes of between 0.8 and 2.1.

The tremors occurred at depths of about 15 to 25 miles (25 to 40 kilometers), close to the boundary between the crust and the mantle, and much deeper than normal crustal earthquakes.

The depth at which the quakes occurred, as well as their low frequency, suggests they might be so-called Deep Long Period earthquakes, or DPLs, which occur in volcanic areas.

"People aren't really sure what causes DPLs," said Amanda Lough, a postdoctoral student in Wiens's lab and the first author of the study, said in a statement.

"It seems to vary by volcanic complex, but most people think it's the movement of magma and other fluids that leads to pressure-induced vibrations in cracks within volcanic and hydrothermal systems."

Why is the discovery important?

Lough and her team say it's not a matter of if the newly discovered volcano will erupt, but when. "It most likely has erupted before," Lough said. (Watch video: Volcanoes 101.)

That's because the volcano sits atop a raised portion of land that the team believes is composed of previously erupted material.

What would happen in an eruption?

The volcano is covered by more than half a mile (one kilometer) of ice, so it would have to be an extraordinarily powerful eruption to breach the surface.

However, the heat from the volcano could increase melting at the base of the glacier and meltwater could act like a lubricant that makes the overlying ice flow out to sea faster. Global sea levels could rise by a small amount as a result.

"We're not talking about an eruption causing the ice sheet to melt and cause catastrophic sea-level rise," Lough told National Geographic.

"This volcanic complex has been operating for millions of years ... There have been past eruptions of this system and the ice has survived for millions of years, [so] future eruptions alone will not cause the ice sheet to fail."

What's next?

Most of the seismometers used to discover the volcano have been removed and installed in other areas in Antarctica, so further study of its seismic activity is no longer possible.

But Lough said she hopes scientists will continue to study the volcano using other instruments.

"I'm really excited because this paper has stirred up a lot of interest in the glaciology community," she said, "and hopefully someone there will take up the challenge to answer the questions of what are the possible outcomes."

http://news.nationalgeographic.com/news ... e-science/

http://www.nature.com/ngeo/journal/v6/n ... o1992.html

[Chromium6]

Cousins Of Titanic-Munching Bacteria Could Aid In Gas And Oil Recovery

By Rebekah Marcarelli r.marcarelli@hngn.com | Dec 19, 2013 03:13 PM EST

Bacteria are slowly eating the Titanic's Iron particles.

Researchers observed remarkable bacteria that can withstand extreme conditions such as heat, pressure, darkness, and incredibly low oxygen levels, the findings could help aid the energy industry.

The bacteria, called Halomonas, lives in sandstone formations that aid in "hydrocarbon extraction and carbon sequestration," a University of Illinois news release reported.

"We are using new DNA technologies to understand the distribution of life in extreme natural environments," said study leader Bruce Fouke, a professor of geology and of microbiology at the University of Illinois at Urbana-Champaign, said

Microbes that live underground are believed to be even more diverse than those that reside on the surface.

"Astonishingly little is known of this vast subsurface reservoir of biodiversity, despite our civilization's regular access to and exploitation of subterranean environments," Fouke said.

The team confirmed their findings by analyzing the bacteria in a sandstone reserve over a mile below the surface.

The researchers performed an analysis of the bacteria's genome.

"[We found that] a low-diversity microbial community dominated by Halomonas sulfidaeris-like bacteria that have evolved several strategies to cope with and survive the high-pressure, high-temperature and nutrient deprived deep subsurface environment," Fouke said.

The analysis revealed the bacteria were able to use iron, nitrogen, and other nutrients in the surrounding sandstone, and recycle them to support their own metabolic health.

A similar form of bacteria Halomonas titanicae are currently eating the famous sunken ship, Titanic, one piece of iron at a time.

The Halomonas sulfidaeris were found to be able to metabolize aromatic compounds, which can be found in petroleum.

"This means that these indigenous microbes would have the adaptive edge if hydrocarbon migration eventually does occur," Fouke said.

"[A better understanding of the microbial life of the subterranean world will] enhance our ability to explore for and recover oil and gas, and to make more environmentally sound choices for subsurface gas storage," he said.

http://www.hngn.com/articles/20030/2013 ... covery.htm

[Anaconda]

Chromium6, thanks for reporting on the abiotic conference.

From reading the conference reports, a clear chemical pathway is proposed, of purely abiotic origin, with strong confirmation of physical observations & measurements at the Mid-Atlantic Ridge.

Keith and Swan provide observations and explanations for hydrocarbon deposits near and within fault patterns remote from the midocean ridges.

Keith and Swan reported an association between the hydrothermal processes that form metallic ore deposits and petroleum occurrences. The authors concluded that this relationship suggests that the petroleum forms as part of a hydrothermal reaction sequence. They noted that these hydrothermal hydrocarbons form at temperatures well above the oil window. Keith and Swan proposed a four-stage process. The first stage is serpentization, which through a series of reactions (e.g., Fischer-Tropsch in the presence of iron-nickel and cobalt catalysts) produces a hydrocarbon-bearing fluid. The second stage is the vertical migration of hydrocarbon-bearing hydrothermal solutions. They suggested that the conduit for this fluid movement is commonly strike-slip faults. The third stage is associated with the hydrothermal diagenesis of reservoirs including the formation of high-temperature (saddle) dolomites. The authors suggested that such fields like Ghawar in Saudi Arabia are possible examples of such hydrothermal deposits. The authors further noted that the dolomitization process itself can be an effective means for creating hydrogen and methane. [...]

Keith and Swan discuss production of hydrogen and methane:

The authors further noted that the dolomitization process itself can be an effective means for creating hydrogen and methane. Keith and Swan stated that several large methane-charged hydrothermal seeps have been identified in transform settings such as Lost City (on the Mid-Atlantic Ridge).

Reported observations, by Charlou et al., at the Mid-Atlantic Ridge, show several high hydrogen and methane discharge areas as discussed by Keith and Swan:

The driving mechanism is fluid circulation, represented by hydrothermal vents associated with slow-spreading midocean ridges. To support this model, marine geology cruises that examined the Mid-Atlantic Ridge were reviewed. Charlou et al. noted the presence of several high hydrogen and methane discharge areas including Rainbow.

Most of this methane was derived through serpentization of ultramafic rocks producing hydrogen, which in turn reacts with CO or CO2 in a Fischer-Tropsch-type reaction to yield hydrocarbons.

Physical confirmation of "the presence of several high hydrogen and methane discharge areas" consistent with the proposed chemical pathway is an example of the superior explanatory power of abiotic analysis when applied to the observed geophysical conditions.

The paragraph below is striking, it is a "rainbow" of hydrocarbons!

The methane produced in this manner is isotopically heavy. In addition to methane, the authors reported the presence of a much larger suite of organic compounds, including alkanes, alkenes, alcohols, aldehydes, ketones, esters, and a collection of cyclic hydrocarbons. At the Rainbow location, compounds with at least 29 carbons have been reported.

Let's let that sink in for hard consideration:

At the Rainbow location, compounds with at least 29 carbons have been reported.

These scientists propose a geophysical process that matches up with the observed physical data at the midocean ridges.

At the midocean ridges, such as the Mid-Atlantic Ridge, is there any realistic biotic or so-called "fossil" fuel hypothetical explanation?

Szatmari, et al. describe a distribution of hydrocarbon chain length observed in both natural oil deposits and Fischer-Tropsch synthetic hydrocarbon production.

For example, they suggested that the Schulz-Flory distribution of n-alkanes, where the log of alkane abundance is linearly related to the carbon number observed on a synthetic petroleum formed through Fischer-Tropsch, and a suite of naturally occurring Brazilian oils are both indicators of polymerization

.

Further discussion of specific catalytic and reactive chemicals and geophysical conditions:

Charlou et al. proposed that minerals such as pyrite, chalcopyrite, and sphalerite act as catalysts for the formation of these higher molecular weight hydrocarbons. They further noted that the degree of polymerization increases with increasing pressure. It was reported that several experimental studies have produced similar organic materials under hydrothermal conditions.

Important note: Controlled laboratory experiments with physical parameters approximating natural hydrothermal conditions produce a similar suite of chemical compounds.

When controlled laboratory experiments reproduce physical results consistent with physical conditions observed in the field, such theories & hypothesis must be given due consideration & attention.

Charlou et al., report the degree of polymerization increases with increasing pressure:

They [Charlou et al.] further noted that the degree of polymerization increases with increasing pressure.

This suggests an increasing chemical reaction efficiency, potentially explaining the high quality natural petroleum found at depth off the coast of Brazil and also the coast of west Africa.

It is refreshing to see the free pursuit of scientific inquiry, the propounding of questions needing answers based on continued and repeated physical observations in the field. The welcome admission of the need for additional data is the cornerstone of valid scientific inquiry.

The authors identified several key questions, including where the organic compounds are synthesized within the ultramafic plumbing system and what the best conditions are for the formation of these organic molecules. The authors concluded that additional data obtained on both fluid and rock samples on and off the ridge axis will be required to obtain the answers to these questions.

The geophysical processes of the world are revealing themselves to scientists who use scientific methodology and follow the observed & measured evidence.

[Anaconda]

Thanks to chrimony on another Thunderbolts Forum board, I saw this scientific report:

(phys.org) December 19, 2013 -- Salty surprise: Ordinary table salt turns into 'forbidden' forms

High-pressure experiments with ordinary table salt have produced new chemical compounds that should not exist according to the textbook rules of chemistry.

The experiments help to explore a broader view of chemistry. "I think this work is the beginning of a revolution in chemistry," Oganov says. "We found, at low pressures achievable in the lab, perfectly stable compounds that contradict the classical rules of chemistry. If you apply rather modest pressure, 200,000 atmospheres – for comparison purposes, the pressure at the centre of the Earth is 3.6 million atmospheres – much of what we know from chemistry textbooks falls apart."

One reason for the surprising discovery is that textbook chemistry usually applies to what we call ambient conditions. "Here on the surface of the earth, these conditions might be default, but they are rather special if you look at the universe as a whole," Konôpková explains. What may be "forbidden" under ambient conditions on earth, can become possible under more extreme conditions.

http://phys.org/news/2013-12-salty-ordi ... idden.html

And another report:

(hngn.com) December 20, 2013 -- 'Impossible' Salt Compounds Like 'Discovering A New Continent'

Researchers made a breakthrough that could change the foundation of chemistry as we know it.

"We found crazy compounds that violate textbook rules -- NaCl3, NaCl7, Na3Cl2, Na2Cl, and Na3Cl," Weiwei Zhang, the lead author and visiting scholar at the Oganov lab and Stony Brook's Center for Materials by Design, said. "These compounds are thermodynamically stable and, once made, remain indefinitely; nothing will make them fall apart. Classical chemistry forbids their very existence. Classical chemistry also says atoms try to fulfill the octet rule -- elements gain or lose electrons to attain an electron configuration of the nearest noble gas, with complete outer electron shells that make them very stable. Well, here that rule is not satisfied."

http://www.hngn.com/articles/20096/2013 ... tinent.htm

There is considerable scientific evidence that hydrocarbon production in the Earth's crust is influenced by pressure and temperature. The presence of diamondoids in natural petroleum suggests high pressure and temperature conditions during formation. Keith and Swan note the presence of diamondoids:

Also, they [Keith and Swan] produced evidence that virtually all oils contain diamondoid compounds, which are temperature and pressure resistant.

And Charlou et al., report multiple chemical compounds with various chemical compositions were found in the Mid-Atlantic Ridge:

The methane produced in this manner is isotopically heavy. In addition to methane, the authors reported the presence of a much larger suite of organic compounds, including alkanes, alkenes, alcohols, aldehydes, ketones, esters, and a collection of cyclic hydrocarbons. At the Rainbow location, compounds with at least 29 carbons have been reported.

As Charlou et al. report that with increased pressure there is an increase in hydrocarbon polymerization, this can be thought of as increased chemical reaction efficiency, similar to the observation that certain physical conditions and amounts of chemical elements available will promote more chemical reaction within the total of the available chemical compounds, sometimes described as a "clean burn".

They [Charlou et al.] further noted that the degree of polymerization increases with increasing pressure.

Could the same processes observed in the controlled laboratory experiments on common salt under high pressure and temperature be at work in geophysical processes of hydrocarbon formation?

In deed, could this same phenomenon be responsible for the large number of minerals found in the Earth's crust?

There are literally thousands of minerals in the Earth's crust, with each species of minerals having multiple similar, yet distinct, chemical structures, often running in series. There are also families of minerals with similar chemical structures.

Per Wikipedia, List of minerals (complete):

The IMA/CNMNC administrates c. 6,500 names, and the Handbook of Mineralogy lists 3,803 species. The IMA Database of Mineral Properties/ Rruff Project lists 4,803 valid species (IMA/CNMNC) of total 4,976 minerals.

http://en.wikipedia.org/wiki/List_of_minerals_(complete)

Whether it is super critical water, which has physical properties that act upon mineral formations in the crust, the presence of diamondoids in natural petroleum, or the suite of alkanes with increasing chain length of hydrogen and carbon chemical bonds, and, now, new laboratory findings of "new chemistry", high pressure and temperature have a tremendous influence on geophysical processes in the Earth's crust.

The scientific study of abiotic hydrocarbon formation in the Earth's crust is smack dab in the middle of this "new chemistry".

The so-called "fossil" fuel theory does not begin to explain hydrocarbon formation in the Earth's crust. In deed, while the "diagenesis" and "catagenesis" claimed to happen in the "fossil" fuel theory is cloaked in the dwindling authority of petroleum geologists, they don't have any hypothetical chemical or energy pathways to account for their theory. It literally is a 19th century theory running into the brick wall of modern 21st century geophysical and chemical observation & measurement.

Abiotic oil analysis does have specific chemical and energy pathways described both qualitatively and quantitatively, with laboratory experiments and field observations validating the theory.

[Anaconda]

These reports discuss only pressure & temperature conditions, but a third axis of observation & measurement is electromagnetic conditions. Dr. Anthony Peratt has described the flame of a fire as a plasma, ephemeral as that, and he has also described molten rock, lava, as a plasma. Conduits for magmatic fluids can act as channels of electric current.

Can high pressure & temperature geochemical reaction fronts and geophysical conduits convey fluids with electrical properties of plasma thus also be channels for geo-electric currents? Would different electrical flows cause different chemical bonding reactions? Would electric currents have an causation effect on chemical reaction speed? Or fluid flow within the conduits? Or act as contributing causation to chemical bonding structure?

The laboratory experiments reported above do not take electromagnetic conditions into consideration, but future experiments could conceivably be constructed which do observe & measure chemical reactions under variable electric current, voltage and ampere conditions, as well as pressure & temperature conditions. Magnetism can also be a variable tested to see if it effects chemical bonding under pressure & temperature.

Field observations could measure subtle differences in electromagnetic signatures for various geologic formations. (Oil exploration & development technologies already observe & measure electromagnetic signatures to determine petroleum deposit characteristics.)

It is accepted fact that significant electric currents flow in the crust below the Earth's surface.

How these electric currents effect the geophysical properties of the Earth's interior is a whole field of study.

[Chromium6]

Found this recently. I agree completely Anaconda that Chrimony's post is very, very interesting since it may open a few perspectives in the Electric Universe:
----


Methane Hydrates only form in Lake Baikal

In freshwater environments, gas hydrates have to date been reported only from Lake Baikal (De Batist et al. 2002), the largest freshwater basin in the world. Here, favourable pressures (cf. maximum depth of 1,642 m) and water temperatures (3.1 – 3.4°C), as well asconsiderable sedimentary organic matter enrichment (average ? org content of 2 dry wt%) promote GH formation. The first samples of methane hydrates were recovered in 1997 at 121 and 161 m below the lake floor, from the BDP-97 (Baikal Drilling Project) borehole drilled in the southern part of the lake (Kuzmin et al. 1998 ).

Later, methane hydrates were sampled from the shallow subsurface at the Malenky and K-2 mud volcanoes (Van Rensbergen et al. 2002;Klerkxetal.2003;Matveevaetal. 2003;Khlystov 2006). To date, six GH areas in the central and southern parts of Lake Baikal have been identified. The sediments in the vicinity of the Lake Baikal mud volcanoes (Klerkx et al.2003;Khlystov 2006) frequently contain breccia, while oxidised and diatomaceous silt layers characteristic of bottom sediments in areas of higher sedimentation are absent. Moreover, cores from the discharge areas are generally saturated with gas, and the surface layers disrupted (Khlystov 2006 ). Breccia consist of more densely packed, drier debris among viscous and oily clays containing gas hydrates. This material differs from the host substrate in its physical and mechanical properties and, especially, its clay content. Consequently, it is carried to the surface from greater depth, as documented by, for example, the occurrence of the ancient diatom genus Tertiarius in the surface layers of a core taken near the Malenky structure. These diatoms were dominant during the Pliocene (2.8 – 2.7 Ma B.P. ) and, given the sedimentation rate in southern Lake Baikal (Bradbury et al. 1994 ), they would today occur at sediment depths of ca. 300 m. Also, Pliocene algae have been found in Holocene sediments in cores taken near the Bolshoy and K-2 mud volcanoes (Zemskaya et al. 2008).

Authigenic carbonate formations have been recovered from near-bottom sediments at GH-bearing mud volcanoes in Lake Baikal (Krylov et al. 2008a). By contrast, bottom sediments not in the immediate vicinity of mud volcanoes are almost carbonate-free (Knyazeva 1954). This lack of calcite formation can be explained in terms of pore water under- saturation (Mizandrontsev 1975; Callender and Granina 1997), resulting from the low alkalinity and calcium concentration of the lake water (average concentrations of HCO3 - and Ca 2+ of 66 and 16.1 mg l - 1 respectively; Falkner et al. 1991). Consistent with these findings, minerals of the series rhodochrosite-siderite occur abundantly only in close proximity to areas of fluid discharge.

http://lin.irk.ru/pdf/9973.pdf

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Turquoise Ice of Lake Baikal:


The Mystery Of Lake Baikal's Oil Leak ( a bit dated but shows that a form of Serpentization occurs also in Fresh water. --CSR)

By Hank Campbell | August 18th 2007 12:07 PM

Called by some the Blue Eye of Siberia and by others the Sacred Sea, Lake Baikal, at more than 5,000 feet ( 1,620 meters ), is the world’s deepest lake. The lake has many other interesting features also. For example, more than 330 rivers flow in but only the Angara flows out.

Even the potential for oil-related environmental disaster along the Eastern Siberia–Pacific Ocean pipeline was enough to get that project moved farther away from one one of UNESCO's world heritage objects.

What do you do when Mother Nature herself starts leaking the oil?

There have always been natural outcrops deep in Lake Baikal that contain oil and occasionally the gooey stuff would seep out and float to the surface in the southern and middle part of the lake. These bitumen spots were usually around three feet wide and were considered a natural event. Fortunately, the lake contains oil-oxidizing bacteria so Baikal's ecosystem controlled the contamination.

In 2003 a large dark spot in the ice showed up - large enough it was seen on satellite images. Researchers were called in from the Institute of Limnology, the Russian Academy of Sciences, the Moscow Institute of Oceanology and the Irkutsk Institute of Geochemistry and what they found was not the usual natural seepage but rather a 1500-feet-high fuel spray, consisting of gas, oil and bottom water.

The researchers took samples of sedimentary rock from nearby cores to investigate the oil and gas content in the samples. The gas consisted of methane (99%) and its homologues: butane, propane, pentane, hexane and others. They determined the oil and gas mixture came into water in the form of gas bubbles which were covered by the oil film.

Their analysis has proved that the leak was generated in the sediments and likely originated from the organic matter that became buried in the water body during the Oligocene and early Miocene epochs.

So Lake Baikal manages to clean up oil spills just fine. Does that mean they were wrong to move the pipeline? No, probably not. There's oil oxidizing bactera and then there's the kind of man-made mess that could ruin even an elegant ecological decontamination system like Lake Baikal's.

http://www.science20.com/hank/the_myste ... s_oil_leak

----

http://en.ria.ru/science/20090703/155422404.html

Mini-subs study mud volcano in Lake Baikal

MOSCOW, July 3 (RIA Novosti) - Submersibles involved in research in Siberia's Lake Baikal have conducted their longest dive yet in the world's deepest lake to study a mud volcano, a local preservation fund spokesman said on Friday.

The Mir-1 and Mir-2 mini-subs, which performed 52 dives last summer, spent 10 and 12 hours at a depth of some 1,400 meters on Wednesday.

"These were the longest dives into Baikal... the longest dives there usually last eight or nine hours," the spokesman said.

Researchers resumed work in June to monitor the lake in its southern parts, near Cape Tolsty. The expedition will then proceed to the north, with plans to conduct research in the lake's central part in July and in northern Baikal in August.

The researchers will begin fish research in the Olkhon Gate strait on Friday, where "there is a very interesting environment, in terms of fish and their behavior."

Research earlier this week found evidence that most of Lake Baikal is much younger than the widely accepted age of 25 million years.

"Baikal as we can see it now, its shoreline, is about 6000-8000 years old, while the lake's deep-water area is about 150,000 years old," a researcher told RIA Novosti.

[Chromium6]

Algae to crude oil: Million-year natural process takes minutes in the lab

December 17, 2013

Tom Rickey, PNNL, (509) 375-3732

Process simplifies transformation of algae to oil, water and usable byproducts

RICHLAND, Wash. – Engineers have created a continuous chemical process that produces useful crude oil minutes after they pour in harvested algae — a verdant green paste with the consistency of pea soup.

The research by engineers at the Department of Energy's Pacific Northwest National Laboratory was reported recently in the journal Algal Research. A biofuels company, Utah-based Genifuel Corp., has licensed the technology and is working with an industrial partner to build a pilot plant using the technology.

In the PNNL process, a slurry of wet algae is pumped into the front end of a chemical reactor. Once the system is up and running, out comes crude oil in less than an hour, along with water and a byproduct stream of material containing phosphorus that can be recycled to grow more algae.

With additional conventional refining, the crude algae oil is converted into aviation fuel, gasoline or diesel fuel. And the waste water is processed further, yielding burnable gas and substances like potassium and nitrogen, which, along with the cleansed water, can also be recycled to grow more algae.
While algae has long been considered a potential source of biofuel, and several companies have produced algae-based fuels on a research scale, the fuel is projected to be expensive. The PNNL technology harnesses algae's energy potential efficiently and incorporates a number of methods to reduce the cost of producing algae fuel.

"Cost is the big roadblock for algae-based fuel," said Douglas Elliott, the laboratory fellow who led the PNNL team's research. "We believe that the process we've created will help make algae biofuels much more economical."

PNNL scientists and engineers simplified the production of crude oil from algae by combining several chemical steps into one continuous process. The most important cost-saving step is that the process works with wet algae. Most current processes require the algae to be dried — a process that takes a lot of energy and is expensive. The new process works with an algae slurry that contains as much as 80 to 90 percent water.

"Not having to dry the algae is a big win in this process; that cuts the cost a great deal," said Elliott. "Then there are bonuses, like being able to extract usable gas from the water and then recycle the remaining water and nutrients to help grow more algae, which further reduces costs."

While a few other groups have tested similar processes to create biofuel from wet algae, most of that work is done one batch at a time. The PNNL system runs continuously, processing about 1.5 liters of algae slurry in the research reactor per hour. While that doesn't seem like much, it's much closer to the type of continuous system required for large-scale commercial production.

The PNNL system also eliminates another step required in today's most common algae-processing method: the need for complex processing with solvents like hexane to extract the energy-rich oils from the rest of the algae. Instead, the PNNL team works with the whole algae, subjecting it to very hot water under high pressure to tear apart the substance, converting most of the biomass into liquid and gas fuels.

The system runs at around 350 degrees Celsius (662 degrees Fahrenheit) at a pressure of around 3,000 PSI, combining processes known as hydrothermal liquefaction and catalytic hydrothermal gasification. Elliott says such a high-pressure system is not easy or cheap to build, which is one drawback to the technology, though the cost savings on the back end more than makes up for the investment.

"It's a bit like using a pressure cooker, only the pressures and temperatures we use are much higher," said Elliott. "In a sense, we are duplicating the process in the Earth that converted algae into oil over the course of millions of years. We're just doing it much, much faster."

The products of the process are:

Crude oil, which can be converted to aviation fuel, gasoline or diesel fuel. In the team's experiments, generally more than 50 percent of the algae's carbon is converted to energy in crude oil — sometimes as much as 70 percent.

Clean water, which can be re-used to grow more algae.

Fuel gas, which can be burned to make electricity or cleaned to make natural gas for vehicle fuel in the form of compressed natural gas.

Nutrients such as nitrogen, phosphorus, and potassium — the key nutrients for growing algae.

Elliott has worked on hydrothermal technology for nearly 40 years, applying it to a variety of substances, including wood chips and other substances. Because of the mix of earthy materials in his laboratory, and the constant chemical processing, he jokes that his laboratory sometimes smells "like a mix of dirty socks, rotten eggs and wood smoke" — an accurate assessment.

Genifuel Corp. has worked closely with Elliott's team since 2008, licensing the technology and working initially with PNNL through DOE's Technology Assistance Program to assess the technology.

"This has really been a fruitful collaboration for both Genifuel and PNNL," said James Oyler, president of Genifuel. "The hydrothermal liquefaction process that PNNL developed for biomass makes the conversion of algae to biofuel much more economical. Genifuel has been a partner to improve the technology and make it feasible for use in a commercial system.

"It's a formidable challenge, to make a biofuel that is cost-competitive with established petroleum-based fuels," Oyler added. "This is a huge step in the right direction."

The recent work is part of DOE's National Alliance for Advanced Biofuels & Bioproducts, or NAABB. This project was funded with American Recovery and Reinvestment Act funds by DOE's Office of Energy Efficiency and Renewable Energy. Both PNNL and Genifuel have been partners in the NAABB program.

In addition to Elliott, authors of the paper include Todd R. Hart, Andrew J. Schmidt, Gary G. Neuenschwander, Leslie J. Rotness, Mariefel V. Olarte, Alan H. Zacher, Karl O. Albrecht, Richard T. Hallen and Johnathan E. Holladay, all at PNNL.

-----------------------------------------------------

Reference: Douglas C. Elliott, Todd R. Hart, Andrew J. Schmidt, Gary G. Neuenschwander, Leslie J. Rotness, Mariefel V. Olarte, Alan H. Zacher, Karl O. Albrecht, Richard T. Hallen and Johnathan E. Holladay, Process development for hydrothermal liquefaction of algae feedstocks in a continuous-flow reactor, Algal Research, Sept. 29, 2013, DOI: 10.1016/j.algal.2013.08.005.

http://www.pnl.gov/news/release.aspx?id=1029

[kiwi]

Chemistry does as good a job as Astrophysics in "hiding" the electrical phenomena in plain site?

In effect, both oceanic and continental Serpentospheres reflect a deep ‘weathering’ process that consists of the interaction of deep crustal and oceanic, water-dominated fluids with the upper portion of a mainly harzburgitic peridotite at the top of the earth’s lithospheric mantle. The process is analogous to the formation of the pedosphere through interactions of the earth’s hydrosphere-atmosphere layer with the top of the earth’s lithospheric crustal layer. In this context, the Serpentosphere may be viewed as a THIN MEMBRANE (My capitals ) that separates water-poor, life-free abiogenetic processes in the mantle from water-rich, life-related processes above the Serpentosphere in the oceanic crust.

The Serpentosphere has enormous and novel implications for four major geologic problems that are of ("current"? ) current interest to the geologic and social community: the driving mechanism for plate tectonics,( Oh really? how? )

Where is the inclusion of the Telluric electrical activity?

These reports discuss only pressure & temperature conditions, but a third axis of observation & measurement is electromagnetic conditions. Dr. Anthony Peratt has described the flame of a fire as a plasma, ephemeral as that, and he has also described molten rock, lava, as a plasma. Conduits for magmatic fluids can act as channels of electric current.

Can high pressure & temperature geochemical reaction fronts and geophysical conduits convey fluids with electrical properties of plasma thus also be channels for geo-electric currents? Would different electrical flows cause different chemical bonding reactions? Would electric currents have an causation effect on chemical reaction speed? Or fluid flow within the conduits? Or act as contributing causation to chemical bonding structure?

The laboratory experiments reported above do not take electromagnetic conditions into consideration, but future experiments could conceivably be constructed which do observe & measure chemical reactions under variable electric current, voltage and ampere conditions, as well as pressure & temperature conditions. Magnetism can also be a variable tested to see if it effects chemical bonding under pressure & temperature.

Field observations could measure subtle differences in electromagnetic signatures for various geologic formations. (Oil exploration & development technologies already observe & measure electromagnetic signatures to determine petroleum deposit characteristics.)

It is accepted fact that significant electric currents flow in the crust below the Earth's surface.

How these electric currents effect the geophysical properties of the Earth's interior is a whole field of study.

Thanks Anaconda, check this out re-water, possibly similar mechanism going on inside the Earth?

http://www.youtube.com/watch?v=q33KyLkP_Rg


And thought this was quite good to see, .. if it hasnt already been posted in here

Cheers

PetroBoss

Joined: Wed Aug 18, 2010 10:15 pm
Posts: 36

Post Re: Electrical generation in Oil reservoirs above saline wat


I’m familiar with tellurics and the externally generated or solar generated large scale currents and associated effect on electro-magnetic field fluctuations. I have experimenting in the AC audio/magno tellurics as an exploration or depth determination tool. Mixed results. I wish those tools were better understood or use in the Oil and Gas community.

The phenomenon I experience was much more localize to the reservoir and of what appeared to be a significant amount of electrical energy.

In light of that I started thinking:
As the world changes from crude based energy to more renewable sources I was wondering if we might be missing an additional clean source of electricity, electricity from underground “fuel cells”.

mr-Oil

Joined: Sun Aug 22, 2010 1:10 am
Posts: 7

Post Re: Electrical generation in Oil reservoirs above saline wat
I think your ideas are really excellent and worth looking into as it may be a very good alternate energy source. Although, IO do think this is simply related to self potential (SP) which is developed between two different lithologies(electrodes in your case) in presence of an electrolyte(any fluid). I wander if that will ever be enough to generate significant amounts of electricity...

http://www.epgeology.com/general-discus ... -t138.html

[Chromium6]

Found this recently. Can't find evidence of anything revised since 2007 for Hyperion's hydrocarbons (like Titan's).

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Hydrocarbon Present on Saturn's Moon Hyperion
Tweet
Tea Lulic | Jul 5, 2007

Hyperion

NASA's Cassini Spacecraft has finally released details about Saturn's moon Hyperion's surface. It turns out, Hyperion is filled with many craters which are filled with hydrocarbons.

When we think about hydrocarbons, we tend to relate it to the Earth. Surely, Earth contains hydrocarbons which are needed for life, but the question that scientists are asking today is whether hydrocarbons can be in fact found on other planets, moons, stars after a recent hydrocarbon discovery on Hyperion.

Hyperion is one of the largest irregular moons in the solar system. It is approximately 300 km across and its surface is absolutely odd-looking.

When the Cassini spacecraft passed by it in September 2005, scientists were able to find out the density of it: an astonishing 0.5 times that of water. If this is hard for you to grasp, think about the rocks. They are about 2-3 times as dense as water. Even ice is 0.9 times the density of water.

"“The close flyby produced a tiny but measurable deflection of Cassini’s orbit. Therefore, the orbit determination, carried out by our Italian colleagues, allowed us to estimate the mass with fairly good accuracy,” said Cassini radio science deputy team leader Nicole Rappaport of the Jet Propulsion Laboratory in Pasadena, Calif. “Combined with the determination of Hyperion’s volume from imaging data, this provided an accurate computation of its density.”"

How can this be possible? One of the hypothesis out there states that Hyperion was actually in the way of other objects which in turn crashed right into it, rupturing the moon, creating cracks and fissures throughout it. Since, in this case, it would have a whole lot of holes, this would account for its very low density. In fact, this might be the lowest density object yet found in the solar system.

If something crashed into a denser body, it would blast material right from it. However, careful analysis of Hyperion's surface shows something totally different: craters were actually formed through compressing the surface. So, basically, the moon can absorb the impact better without disturbing the neighbouring terrain. In simple terms, whatever happens when you are punching a piece of Styrofoam happens on Hyperion.
Moreover, because the moon has very low gravity, the material that crashes into it and is ejected from the craters has a very good chance of completely escaping and not impacting its surface again. Thus, Hyperion's craters look rather sharp and less blanketed by debris compared to other bodies' craters found in space.
What is even more fascinating about this moon is that it contains water, carbon dioxide ice and dark material which fits in the profile of hydrocarbons.

""Of special interest is the presence on Hyperion of hydrocarbons--combinations of carbon and hydrogen atoms that are found in comets, meteorites, and the dust in our galaxy," said Dale Cruikshank, a planetary scientist at NASA's Ames Research Center, Moffett Field, Calif., and the paper's lead author. "These molecules, when embedded in ice and exposed to ultraviolet light, form new molecules of biological significance. This doesn't mean that we have found life, but it is a further indication that the basic chemistry needed for life is widespread in the universe.""

Cassini's ultraviolet imaging spectrograph captured different compositional variations found on Hyperion's surface. After analyzing its surface, these instruments sent back data confirming that there is a presence of frozen water but it also discovered solid carbon dioxide also known as dry ice. Oddly enough, dry ice was mixed with the ordinary ice.


An image to your right shows the presence of dry ice and frozen water. Blue shows the maximum exposure of frozen water; red is the dry ice; magenta are regions of water and carbon dioxide; and yellow is a mix of carbon dioxide and yet unidentified material.

""Most of Hyperion's surface ice is a mix of frozen water and organic dust, but carbon dioxide ice is also prominent. The carbon dioxide is not pure, but is somehow chemically attached to other molecules," explained Cruikshank."
Scientists took a look at the previous data from other Saturn's moons, as well as Jupiter's moons Ganymede and Callisto and compared this data to the one retrieved from Hyperion. It points out that carbon dioxide molecule is "complexed" or attached to other surface material in many different ways.
""We think that ordinary carbon dioxide will evaporate from Saturn's moons over long periods of time," said Cruikshank, "but it appears to be much more stable when it is attached to other molecules.""
Hyperion is known for its chaotic spin. It is also Saturn's eighth largest moon and orbits Saturn every 21 days.

http://m.digitaljournal.com/article/203180
You can find full research and analysis of Hyperion's surface in July 5 issue of Nature magazine.

[StefanR]

Found this recently. Can't find evidence of anything revised since 2007 for Hyperion's hydrocarbons (like Titan's).

Does this refer in some way to the supposed tholin production/distribution in the outer solarsystem?
As is related to here:

During Cassini's first encounters with Titan, the INMS revealed an atmosphere dominated by nitrogen and methane. Of significance from measurements taken in later flybys, however, was the detection of benzene, a critical component in the formation of aromatic hydrocarbon compounds. At the same time, two other Cassini sensors that are part of the Cassini Plasma Spectrometer (CAPS) investigation, the Ion Beam Spectrometer (IBS) and Electron Spectrometer (ELS), measured large positive and negative ions.

The negative ions were a complete surprise," said Dr. David Young, also an SwRI Institute scientist, and leader of the CAPS investigation. "This suggests they may play an unexpected role in making tholins from carbon-nitrogen precursors."

http://www.astrobio.net/pressrelease/2330/making-tholins


As a side note came across some old links and citations in the electric comet thread concerning electric
conductivity/resistivity of carbon/petro-stuffings in the ground:

Electrical properties of Precambrian Tien Shan rocksand their thermophysical-chemical activity at highpressures and temperatures
http://66.102.9.104/search?q=cache:-Hg0 ... cd=9&gl=nl
Quote:
The most important result of our analysis of the dis-tribution of the thermoactive rocks over the three zonesis the increased concentration of these rocks found inthe seismic zone itself, i.e., in the South Tien Shan re-gion. Among the 19 rocks studied, 9 samples exhibit the electric resistivity anomalies, with 8 of them belong-ing to the region mentioned above. This suggests that higher seismicity is related to the petrophysical features of geomaterials.


Electrical conductivity and carbon in metamorphic rocks of the Yukon-Tanana Terrane, Alaska
http://www.osti.gov/energycitations/pro ... _id=245147
Quote:
The stringer is probably responsible for the anomalous conductivity change with pressure, making the sample the first for which anomalous electrical conductivity behavior can be attributed to carbon associated with a specific feature.
The observations indicate that carbonaceous material may exert a primary control on crustal electrical conductivity because it may be present as interconnected arrays in grain boundaries or microfractures or in megascopic, throughgoing fractures.

http://www.thunderbolts.info/forum/phpBB3/viewtopic.php?f=4&t=4158&start=75#p337

[Chromium6]

This might not be the best source but this theory is developing. Might explain inexplicable layers of Carbon-coal in places where it should not exist:

-------
Does Titan Rain Methane?
http://www.astrobio.net/interview/1413/ ... in-methane

-------------------------
(That's a lot of Carbon from their models!)

Asteroid Impact Created a Worldwide Rain of Carbon Beads

by Fraser Cain on May 6, 2008

When a large enough asteroid strikes the Earth, the devastation effects the entire globe. And the dinosaur-killing asteroid that smashed into the Yucatan peninsula 65 million years ago was no exception. According to researchers, just one outcome from the strike: carbon in the Earth’s crust was liquified and formed tiny beads that rained back down across the entire planet.
....

And the cenospheres have been discovered around the planet next to the iridium layer, in Canada, Spain, Denmark and New Zealand. The key discovery is that the cenospheres get smaller as you move away from the impact site. This matches the prediction that the heavier particles would rain back down to Earth closer to the impact, while the lightest particles would be carried across the entire planet.

The researchers were able to calculate the total amount of carbon injected into the atmosphere from an asteroid impact, and put the number at 900 trillion tonnes. This helps scientists get a better estimate of the impact size and damage.

http://www.universetoday.com/14077/aste ... bon-beads/

--------------------------
27 October 2011
Stars manufacturing complex organic matter?
by Kate Melville

An analysis of the spectral emissions from distant stars suggests that compounds of unexpected complexity - some resembling coal and petroleum - exist throughout the universe and are being made by stars. The proponents of this controversial idea, Professors Sun Kwok and Yong Zhang of the University of Hong Kong, argue their case in the current issue of the journal Nature.

Kwok and Zhang base their hypothesis on a set of infrared emissions - known as "Unidentified Infrared Emission Features" - previously detected in stars and interstellar space. Since the first recording of these emissions, the most commonly accepted theory regarding their origin has been that they come from simple organic molecules made of carbon and hydrogen atoms, known as polycyclic aromatic hydrocarbons (PAH).

Kwok and Zhang contend, however, that observations from the Infrared Space Observatory and the Spitzer Space Telescope indicate that these spectra have features that cannot be explained by PAH molecules alone. Rather, they propose that the substances generating these spectra have chemical structures that are much more complex. By analyzing the emissions of star dust formed in exploding stars, they claim that stars are making these complex organic compounds in timeframes of only weeks.

The scientists add that not only are stars producing this complex organic matter, they are also ejecting it into interstellar space. "Our work has shown that stars have no problem making complex organic compounds under near-vacuum conditions," said Kwok. "Theoretically, this is impossible, but observationally we can see it happening."

Kwok says that the compounds are so complex that their chemical structures resemble those of coal and petroleum. Coal and oil are thought to arise only from living organisms but the tell-tale spectra, he argues, show complex organic compounds can be synthesized in space even when no life forms are present.

Kwok and Zhang's work raises the possibility that stars enriched the early solar system with complex organic compounds. The early Earth was subjected to bombardment by comets and asteroids, which may have been delivery vehicles for this organic star dust. Whether these organic compounds played any role in the development of life on Earth remains an open question.

http://www.scienceagogo.com/news/201109 ... _sys.shtml

[Chromium6]

More articles on seawater contacting magma under the oceans in hydrated fault zones.
------

Is there an ocean beneath our feet?

by Staff Writers
Liverpool, UK (SPX) Feb 03, 2014


Summary of subduction zone structure inferred for waveform modelling of dispersed P-wave arrivals. Image courtesy Garth and Rietbrock, Geology, 2014.

Scientists at the University of Liverpool have shown that deep sea fault zones could transport much larger amounts of water from the Earth's oceans to the upper mantle than previously thought.

Water is carried mantle by deep sea fault zones which penetrate the oceanic plate as it bends into the subduction zone. Subduction, where an oceanic tectonic plate is forced beneath another plate, causes large earthquakes such as the recent Tohoku earthquake, as well as many earthquakes that occur hundreds of kilometers below the Earth's surface.

Seismologists at Liverpool have estimated that over the age of the Earth, the Japan subduction zone alone could transport the equivalent of up to three and a half times the water of all the Earth's oceans to its mantle.

Using seismic modelling techniques the researchers analysed earthquakes which occurred more than 100 km below the Earth's surface in the Wadati-Benioff zone, a plane of Earthquakes that occur in the oceanic plate as it sinks deep into the mantle.

Analysis of the seismic waves from these earthquakes shows that they occurred on 1 - 2 km wide fault zones with low seismic velocities. Seismic waves travel slower in these fault zones than in the rest of the subducting plate because the sea water that percolated through the faults reacted with the oceanic rocks to form serpentinite - a mineral that contains water.

Some of the water carried to the mantle by these hydrated fault zones is released as the tectonic plate heats up. This water causes the mantle material to melt, causing volcanoes above the subduction zone such as those that form the Pacific 'ring of fire'. Some water is transported deeper into the mantle, and is stored in the deep Earth.

"It has been known for a long time that subducting plates carry oceanic water to the mantle," said Tom Garth, a PhD student in the Earthquake Seismology research group led by Professor Andreas Rietbrock.

"This water causes melting in the mantle, which leads to arc releasing some of the water back into the atmosphere. Part of the subducted water however is carried deeper into the mantle and may be stored there.

Large amounts of water deep in the Earth

"We found that fault zones that form in the deep oceanic trench offshore Northern Japan persist to depths of up to 150 km. These hydrated fault zones can carry large amounts of water, suggesting that subduction zones carry much more water from the ocean down to the mantle than has previously been suggested.

"This supports the theory that there are large amounts of water stored deep in the Earth."

Understanding how much water is delivered to the mantle contributes to knowledge of how the mantle convects, and how it melts, which helps to understand how plate tectonics began, and how the continental crust was formed.

http://www.spacedaily.com/reports/Is_th ... t_999.html

-----------

'Anti-plume' Found Off Pacific Coast

Date:
July 15, 2004

Source:
Oregon State University

Summary:
A North American team of scientists has documented for the first time a new phenomenon -- the creation of a void in the seafloor that draws in -- rather than expels -- surrounding seawater.


The gradual subduction of the Juan de Fuca plate beneath the North American plate puts tremendous stress on the seafloor, creating cracks and fissures, hydrothermal vents, seafloor spreading, and literally hundreds of small earthquakes on a near-daily basis.

Now a North American team of scientists has documented for the first time a new phenomenon – the creation of a void in the seafloor that draws in – rather than expels – surrounding seawater.

They report their discovery in the July 15 issue of the journal Nature.

Oregon State University oceanographer Robert Dziak said the discovery is important because it adds a new wrinkle to scientific understanding of seafloor spreading, the fundamental process of plate tectonics and the creation of ocean crust. Dziak has a dual appointment with the National Oceanic and Atmospheric Administration's Pacific Marine Environmental Laboratory.

"Just when you think you're beginning to understand how the process works, there's a new twist," Dziak said. "There was an episode of seafloor spreading on a portion of the Juan de Fuca Ridge that was covered with about a hundred meters of sediment and what usually happens in that case is that lava erupts onto the ocean floor and hot fluid is expelled into the water.

"In this case, though, it actually drew water down into the subsurface, which is something scientists have never before observed," he said.

The research team included Earl Davis, of the Geological Survey of Canada's Pacific Geoscience Centre; Keir Becker, from the Rosenstiel School of Marine and Atmospheric Science at the University of Florida; Dziak; and John Cassidy, Kelin Wang and Marvin Lilley of the University of Washington.

Dziak said the researchers think the seafloor spreading caused the ocean crust to dilate, increasing the pore space much like a sponge. "It's like an anti-plume," he said. "Instead of sending materials from within the Earth to the ocean floor, it simply sucks down the surrounding seawater."

The researchers aren't sure exactly what causes the dilation, but it has multiple implications. First, it changes how scientists view seafloor spreading since there isn't an automatic outpouring of lava, or hot liquid via hydrothermal vents previously associated with tectonic plate theory.

The size of these potential "voids" also intrigues scientists, who wonder how much seawater can be subsumed. If large, or frequent, they could affect surrounding water temperatures and chemical composition, Dziak said.

Finally, water migrating downward through the Earth may be enough to trigger the growth of bacteria at startling depths. Last year, in an unrelated study, OSU oceanographer Martin Fisk and a team of researchers found bacteria in a hole drilled 4,000 feet through volcanic rock. Basalt rocks have all of the elements required for life, Fisk pointed out, including carbon, phosphorus and nitrogen. Only water is needed to complete the formula.

Dziak is able to monitor offshore activities from his laboratory at OSU's Hatfield Marine Science Center in Newport, where he uses an array of undersea hydrophones through a unique arrangement with the U.S. Navy. During the past dozen years, Dziak and his research team have recorded more than 30,000 earthquakes in the Pacific Ocean off the Northwest coast – few of which have ever shown up on land-based seismic equipment.

http://www.sciencedaily.com/releases/20 ... 075917.htm


----------


Shimmering water reveals cold volcanic vent in Antarctic waters

Date: February 6, 2013

Source: National Oceanography Centre

Summary: The location of an underwater volcanic vent, marked by a low-lying plume of shimmering water, has been revealed.

The location of an underwater volcanic vent, marked by a low-lying plume of shimmering water, has been revealed by scientists at the National Oceanography Centre, Southampton.

Writing in the journal PLOS ONE the researchers describe how the vent, discovered in a remote region of the Southern Ocean, differs from what we have come to recognise as "classic" hydrothermal vents. Using SHRIMP, the National Oceanography Centre's high resolution deep-towed camera platform, scientists imaged the seafloor at Hook Ridge, more than 1,000 metres deep.

The study, funded by the Natural Environment Research Council (NERC), aimed to build on our knowledge of how deep-sea creatures associated with hydrothermal activity evolve and migrate between different regions.

Hydrothermal vents are like hot springs, spewing jets of water from the seafloor out into the ocean. The expelled water, if hot enough, is rich in dissolved metals and other chemicals that can nourish a host of strange-looking life, via a process called "chemosynthesis." The hot water, being more buoyant than the surrounding cold seawater, rises up like a fountain or "plume," spreading the chemical signature up and out from the source.

The Hook Ridge vent, however, was found to lack the high temperatures and alien-like creatures that we now associate with hot hydrothermal vents. Instead there was a low-lying plume of shimmering water, caused by differences relative to the surrounding seawater in certain properties, such as salinity.

http://www.sciencedaily.com/releases/20 ... 093900.htm

[Chromium6]

Direct Conversion of Algal Biomass Under Supercritical Methanol and Microwave Irradiation Conditions

Chemical Engineering Department
Electron Microscopy Lab

Las Cruces, NM 88003
Solix Biofuels, 430-B North College Ave, Fort Collins, CO 80524

One-Step Conversion of Wet Algae

Why Wet Algae?
• Residual water in Wet Algae becomes
an excellent organic solvent
at near-critical conditions and is non-toxic.
• Conversely, removing residual water from algal biomass is
expensive and energy demanding.

Why Supercritical Methanol ?
Single-Step Conversion Process
Simultaneous Extraction and Transesterification !!
• Non-catalytic-Simpler purification of products
• Lower reaction time and More environmental friendly

http://www.tappi.org/content/Events/11B ... 1Patil.pdf

http://www.supercriticalfluids.com/wp-c ... ioxide.pdf

------------
http://www.formatex.info/energymaterial ... 64-268.pdf

Gasification of biomass in supercritical water (SCWG)
A. Möbius, N. Boukis and J. Sauer

Institute of Catalysis Research and Technology, Karlsruhe
Institute of Technology (KIT),
Hermann-von-Helmholtz-Platz
1, 76344 Eggenstein-Leopoldshafen, Germany


3. Supercritical water gasification

3.1 Supercritical water gasification of model substances Glucose serves as a model substance, because it mimics the composition of the carbohydrates contained in biomass.

Decomposition of glucose in supercritical water runs following this reaction: C 6 H 12 O 6 + 6 H 2 O? 6 CO 2 + 12 H 2(1).

Yu et al. found, that Glucose at low concentrations (0.1 M) can be completely gasified after 34s at 600°C and 34.5 Map [3]. Besides hydrogen and carbon dioxide, methane and carbon monoxide, also trace amounts of ethane and ethane were produced. At higher concentrations of glucose the gas yields are decreasing except for carbon monoxide.

For SCWG of 0.1 M glucose at 600°C, 34.5 MPa and 34 s reaction time in a reactor made of Inconel a total gas yield of 14 mol/mol was reached. No char or tar products were detected. Another main component of biomass is cellulose. After hydrolysis in supercritical water glucose is formed. Resende et al. studied the influence of temperature, concentration and reaction time [4, 5]. They used quartz capillary tubes as mini-batch reactors to avoid influence of the reactor material on the reaction. The longer the reaction proceeds less carbon dioxide and carbon monoxide is produced. On the other hand the share of hydrogen and methane increases. With increasing temperature the yield of all gases is increasing, but the composition of the product gas is changing. As for a longer reaction time the share of hydrogen and methane is increasing and the share of carbon monoxide and carbon dioxide is decreasing. The cellulose loading is an important cost factor as higher concentrations of biomass will reduce the capital and operating costs for the process. Both the composition of the product gas as the gas yields are affected by increasing cellulose concentration. Methane is the major pro duct at low cellulose concentrations, but with increasing cellulose concentrations the mole fraction of methane is declining and the mole fractions of carbon monoxide and hydrogen increases. For SCWG of 9 wt. % cellulose at 600° C, a water density of 0.08g/cm³ and 5 minutes reaction time a total gas yield of 15 mmol/g was reached. At the internal walls of the quartz reactors low amounts of char were found.

A further main component of biomass is lignin. It is a natural organic polymer with an irregular structure, which is thermoplastic and completely insoluble in solvents [6]. Re sende et al. found comparable influence of temperature, reaction time and concentration on the gas yields for cellulose and lignin [5, 7]. Only the hydrogen yield decreases with increasing lignin loading, while it increases with increasing cellulose loading. The total gas yield was lower than for cellulose. For SCWG of 9 wt. % lignin at 600°C, a water density of 0.08g/cm³ and 45 minutes reaction time a total gas yield of 11 mmol/g was reached. Also low amounts of char at the internal walls of the quartz reactors were found. Weiss-Hortala used phenol as an intermediate of lignin hydrolysis [8]. They found the same influence on the total gas yield and the hydrogen yield during the gasification of glucose.


DiLeo et al. used glycine as model substance for animal derived material [9].

Temperature seems to have a lower influence on gasification efficiency as they found in the aqueous phase almost the same amount of residual carbon at 500 and 600°C. The gas yields also did not change much with increasing reaction time. For SCWG of 10 wt. % glycine at 500°C, a water density of 0.079g/cm³ and 60 minutes reaction time a total gas yield of 0.25 mol gas/mol glycine was reached. In the quartz reactors a solid, black residue was found.

3.2 Supercritical water gasification of real biomass

In the last years more and more experiments with real biomasses were conducted. Besides agricultural products like corn and grass [10, 11] also industrial residues like sewage sludge [12] and pyroligneous acid [13] and increasingly algae [14-18] are subject of interest. Kruse et al. studied the influence of different types of proteins on the gasification and found in general low gas yields for protein containing biomass, but differences between biomasses originating from plants and those containing meat.
Animal biomass produces much smaller relative gas yields than vegetable biomass [19].

Depending on the composition of the feed (share of carbohydrates, lignin, proteins, water) the gasification efficiency for these biomasses is different. D'Jesus showed, that even the same kind of biomass (corn in this case) causes different results during gasification depending on the exact species and the conditions of growth of the crops [20]. For aqueous feeds like sewage sludge, pyroligneous acid, but also algae gasification in supercritical water seems to be more suitable for gasification as no further water has to be added to the reaction mixture.

3.3 Apparatus

For laboratory scale experiments three different kinds of reactors are reported in literature: batch reactor (e.g. quartz capillary tubes [5, 16]), semi-batch reactor (e.g. continuously stirred tank reactor CSTR [19]) and continuous reactor (e.g. plug flow reactor PFR [3, 21]). Most of the materials of construction have an influence on the experimental results. The only reactor material reported in literature which seems to be inert under the reaction conditions of supercritical gasification is quartz. Typical material of construction for reactors dealing with supercritical water are nickel base alloys like Inconel and Hastelloy. The yields of all gases, especially the yield of hydrogen were higher in a reactor made out of Inconel compared to reactions performed in a reactor which was made out of Hastelloy [3].

The pilot plant VERENA of the Karlsruhe Institute of Technology (KIT) allows experiments with a maximum throughput of 100kg/h, at up to 700°C and 35 MPa [22, 23]. Both agricultural wastes (herbage [21]) and industrial wastes (pyroligneous acid [22]) as well as feeds which could be used as feed for animal (corn silage [22]) or as direct fuel (ethanol [22]) have been successfully converted.

3.4 Catalysis

Resende et al. studied the effect of metals as catalyst for the gasification of cellulose and lignin in supercritical water [24]. All metals which have been applied (Nickel, Copper, Iron and Ruthenium) showed for cellulose and lignin (Ruthenium was not examined) higher hydrogen yields. Similar results found Chakinala et al. for SCWG of algae with the addition of different metals [16]. All used catalyst (Inconel powder, NiMo, Ni wire, CoMo, Ru/TiO 2 , PtPd) increased the gasification efficiency, especially the Ru/TiO 2 catalyst, with which a yield of hydrogen of 100% was reached. DiLeo observed deactivation of the nickel catalyst during experiments with methanol as feed [25].

Catalysts which consisted of different kinds of carbon were described by Xu et al. [26]. They used different carbon sources as coconut shell, charcoal, coal and macadamia shell and feeds like cell obiose, glycerol, bagasse liquid extract and sewage sludge. For all feeds and catalysts they found an improvement of the gasification results. After less than 4 hours deactivation of the carbon as catalyst was observed. Besides the heterogeneous catalysis of metals and carbon described above, alkali are known for their catalytic properties. After addition of KOH or K 2 CO 3 a product gas rich in hydrogen and carbon dioxide is obtained, because the water-gas shift reaction is catalysed by potassium [27]. This can be applied to carbohydrates, aromatic compounds, glycine and real biomass. Pyrocatechol, a model substance for lig nin, is also almost completely gasified in the presence of KOH [28]. Also Na 2 CO 3 is well known for catalytic effects during cellulose gasification, which result in a higher gasification efficiency [29].

3.5 Other factors influencing the supercritical gasification of biomass

Besides the parameters already discussed as temperature, reaction time, concentration, heterogeneous and homogeneous catalysis, also the heating rate of the biomass seems to influence the gas yield. Matsumura et al. found a higher gasification efficiency at higher heating rates without changes in the gas composition [30]. Sinag et al. studied the influence on the formation of intermediates and detected a lower influence of catalysts on gas formation at higher heating rates [31].


________________________________________________________________________
D'Jesus et al. studied the influence of the particle size of the feed materials to the supercritical water gasification with corn silage [20]. They found a higher hydrogen yield for finer particles and a conversion which increased by 20% due to a decrease in particle size by 50%.

4. Conclusion and prospect

Gasification of biomass in supercritical water is a promising technology for the future [32-35]. The properties of supercritical water allow decomposition of organic matter at high rates. Waste streams of biomass or aqueous biomass like algae can be processed. The product gas consisting mainly of hydrogen, methane and carbon dioxide is generated at high pressure, which allows further utilisation of the product gases without compression. Evaluation of the process showed a lower environmental impact potential than anaerobic fermentation in case of a combined production of hydrogen and methane [36]. On the other hand the costs of the product gas are still higher than other already available fuel gases [37].

Calzavara et al. pointed out, that the recovery of the process water is an important factor for the efficiency of the process [38]. Gasafi et al. concluded, that sewage sludge may be a potential market for SCWG [39].

The utilisation of solar energy as heat source for supercritical water gasification may be the next step to make this process even more sustainable [40]