Wednesday, June 11, 2008

Lack Of C13 Isotope Proves Nothing

The key claim for the theory of biogenic petroleum origin is that low concentrations of the C13 isotope are proof of biogenic origin because photosynthesis preferentially selects C12 over C13.

See Richard Heinberg's The Abiotic Oil Controversy.

Geologists trace the source of the carbon in hydrocarbons through analysis of its isotopic balance. Natural carbon is nearly all isotope 12, with 1.11 percent being isotope 13. Organic material, however, usually contains less C-13, because photosynthesis in plants preferentially selects C-12 over C-13. Oil and natural gas typically show a C-12 to C-13 ratio similar to that of the biological materials from which they are ASSUMED [Emphasis added] to have originated. The C-12 to C-13 ratio is a generally observed property of petroleum and is predicted by the biotic theory; it is not merely an occasional aberration.
Also see Ugo Bardi & Dale Allen Pfeiffer's No Free Lunch.

The isotopic ratios of a substance (particularly the ratio of carbon and hydrogen isotopes) provide us with a profile of the substance, a sort of isotopic fingerprint which indicates how the substance was generated. Most naturally occurring carbon is isotope C-12, with a small percentage of C-13 (1.11%) and a trace of radioactive isotope C-14. Organic matter, however, has a lower ratio of C-13 because photosynthesis preferentially concentrates C-12. Hydrocarbon reserves reflect their organic origin in their C-12/C-13 ratio.
This all comes from the biogenic geologist Barbara Sherwood Lollar's paper: Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons.
Given the fact that geologists know nothing of the universe we live in and given the fact that these individuals are factually challenged I was highly suspicious of this claim. What I discovered is that a lack of C13 isotope proves nothing: Hydrocarbons in Hydrothermal Vent Fluids.

We did, however, observe anomalous amounts of m/z 31 (13C12CH6aq) (relative to that predicted from natural [biogenic] carbon abundances)
How are biogenic theorists going to explain this so-called anomaly?

Is methane the first direct sign of extra-terrestrial life?

The C-12 to C-13 ratio of methane alone is not always proof of life. For example, the "Lost City" hydrothermal vent field in the Atlantic Ocean did not show a clear isotope signature, says James Kasting, professor of earth and mineral science at Penn State University.

"The methane is not that strongly fractionated, but they still think it might be biological," says Kasting. "At Lost City, you can't figure out if it's biological or not by the isotopes. How are we going to figure that out on Mars?"
Carbon stars which are totally deficient in C13 have been observed: The Abundance Ratio of C12 and C13 in Carbon Stars.

Two hydrogen deficient carbon stars HD13716 and HD182040 show no trace of C13N features.
Needless to say, there is no photosynthesis occuring on those stars. And the authors conclude with the following:

The above results revealed that C12/C13 ratio in carbon stars shows a wide range of variety.
John Valley, Geology professor at the University of Wisconsin also admits lack of C13 proves nothing.

High C-12 to C-13 ratios, he says, "when present in sufficient quantity, are very strong evidence of organic activity, although I don't use the word 'proof.'"
So there you have it: lack of C13 proves, you guessed it, absolutely nothing.

Abiogenic hydrocarbons with low C13 content have also been observed in Japan so the "scientists" conclude they must be a mix of biogenic and abiogenic hydrocarbons.

The isotope composition of methane and the relationship between methane/ethane ratio and δ13C-value of methane suggest that these light hydrocarbon gases are mixtures of thermogenic and abiogenic components. The abiogenic hydrocarbon may be attributed to magmatic hydrocarbon gases equilibrated with carbon dioxide at fO2 defined by the fayalite-magnetite-quartz buffer (FMQ)
The reality is that in 2007 ICP-MS showed that all oil has inorganic geochemistry: The Inorganic Geochemistry of Oil.

Of course the final nail in the coffin would have to be this gem from Giardini and Melton (1991): EVIDENCE THAT STABLE CARBON ISOTOPES ARE NOT A RELIABLE CRITERION FOR DISTINGUISHING BIOGENIC FROM NON-BIOGENIC PETROLEUM

The isotopic abundance of presumably-pristine primordial carbon has been determined by analyzing carbon dioxide entrapped in a 8.65 carat natural diamond of African origin. The results were 12C = 98.9275% and13C = 1.0725%, which giveδ13C = -35.2‰/00. This value is well within the range used to assign a biogenic origin to carbon-containing compounds, i.e., more negative than -18.0‰/00. Similar negative values have been reported for some natural diamonds and carbon-bearing meteorites. It is concluded, therefore, that stable carbon isotopes can be an unreliable criterion for assigning a biogenic origin to petroleum.


Anaconda said...

1. Isotopic ratios
2. Bio-markers
3. "source rocks" and the bio-marker finger print.

Dismissal of Claims of a Biological Connection for Natural Petroleum,
J.F. Kenney, et al., 2001
(Available by direct link at left-hand column, under Technical Papers)

Petroleum: To Be Or Not To Be Abiogenic,
M.R. Mello, J.M. Moldowan, 2005
(Available by direct link at left-hand column, under Molecular Daimondoids: Abiomarkers In Oil, listed as Biogenic Cult Says Diamonds formed From Fossils)

Eugene Coste,
...Rock Disturbances...(1914).
(Available by direct link at left-hand column under Eugene Coste)

(OIM) Post, Zack's Bullish On Halliburton, May 13, 2008, Comment #3, Objection to Postulate: Diamond Fingerprint Proves Abiogenic Oil, 5/20/08.

(OIM) Post, Barron's: National Oilwell Varco Ranked 3rd, May 12, 2008, Comment #1, Bio-Marker Argument for "Fossil" Theory Falls Flat..., 5/13/08.

(OIM) Post, Terrorists Dictators Keep Production Artificially Low, June 6, 2008, Comment #3, "Source Rocks", the Ace in the Hole for Fossil theory?, 6/7/08.

Doing the difficult is required of the scientific method. Who wants to point out the strongest claims of the opposing side of the debate?

But that's exactly what has to be done.

"Fossil" theory relies on three claims that advocates claim proves "fossil" theory.

This writer calls these proofs, the three "Aces" of fossil theory.

In fact, "fossil" advocates make the following claim:

...[C]an provide irrefutable proof that 99.99999% of all oil and gas accumulations found up to know(sic) in the planet earth have a biogenic origin." (Mello and Moldowan)

This is a big claim. Does it stand up under inspection?

This writer will endeavor to show the claim not only doesn't stand up, but is highly suspect.

The three "aces" of fossil theory are as follows:

1. Isotopic ratios of C12/C13 show that oil is organic.
2. Biomarkers are remnant molecules of organic detritus in oil.
3. "Source rocks" have the same biomarkers as the oil in reservoir traps which identify the oil like a "finger print."

This post demonstrates that isotopic ratios are variable in terrestrial, stellar, and interstellar environments. So isotopic ratios are not the "silver bullet" claimed by fossil theory.

Further, J.F. Kenney analyses and deconstructs the isotopic ratio argument in the referenced paper, as well as this writer in the 5/20/08 comment. The isotopic argument does not hold up to any scientific scrutiny.

In short, traveling from the mantel to reservoir depths strips C13 out of the hydrocarbon molecule, this contention is supported by experiments reported by Kenney. And sitting in one place can add C13 to hydrocarbons, as supported by Kenney.

The conclusion is inescapable: Isotopic ratios are unreliable and not indicative of hydrocarbon's origin.

So much for that "Ace."

Again, J.F. Kenney analyses and dissects the bio-marker argument, pointing out that while there are molecues that have some similarity, the differnces are dispositive. As does this writer echo that proof. These chemicals are also found in meteorites and are able to be created in the lab, leaving the bio-marker argument, again, less than a "silver bullet."

So much for that "Ace."

Finally, the "source rock" argument. This is a combination argument, saying that bio-markers can be traced from "source rocks" to the oil in the reservoir deposit creating a so called finger print tying the oil to the "source rock."

First, as Mr. Coste demonstrates, "source rock" can't be the source for the oil as trapping rocks are impermiable, therefore, there is no possibility that oil can migrate out of this rock, echoed by this writer. Second, the oil travels from below, originating from a "Source fault" and uses the trapping rock, also called capstone as a conduit from the "source fault" to the reservoir trap, so on the course of the journey through the shale "roof" conduit residue of the oil is left on the caprock. The residue has the miss-called bio-markers in it, so this residue is found on shale conduit or "roof" rock.

Again, this is hardly a "silver bullet" as advertised by fossil theory advocates.

So much for the third "Ace."

And, so much for all these claims being added together, so that they prove "fossil" theory 99.99999%.

Actually, when such certainty is claimed, on less than ironclad evidence, one should always be suspicious. It sounds vaguely like a snake oil saleman or a carnival barker.

And, so, after reasonable scientific scrutiny, the three "Aces" look like they are cards "slipped up their sleeve," in an attempt to bully their claims, when the "poof" is underwhelming at best.

Certainly, all pretense at following scientific method has been abandoned, and like a poker player down on his luck, and desperate for a winning hand, even if he has to pull three aces out of his breast pocket and slip 'em up his sleeve, he'll do it.

And this constitutes 99.99999% proof...Please.

But that has been the entire history of oil geologists -- overstating the evidence and overstating their claims based on that evidence.

Crooked card players eventually get caught. And what happens outside the backside of the saloon is not a pretty sight to watch.

Mello and Moldowan are crooked card players. And they aren't the only cheats in the oil geologist community.

Anaconda said...

(the coup de grace of abiotic oil?)

No Free Lunch, Part 3 of 3: Proof,
Ugo Bardi, Dale allen Pfeiffer, 2005.

Editorial Note: The below check list was meant as the coup de grace, or final denouncement, for abiotic oil theory. It's reproduced, here, with answers for the readers consideration, and as an obligation to list and discuss objections to a proposed theory as required by The Scientific Method.

"In closing, we turn to the eminent Australian astrobiologist and geologist, Dr. Jonathan Clarke. Dr. Clarke has produced a list of 16 observations which must be explained by abiotic hypothesis before it can be seriously considered."

Dr. Clarke's list as follows:

To deny this [that 99.99999% of the world's liquid hydrocarbons are produced by maturation of organic matter] means you have to come up with good explanations for the following observations.

1) The almost universial association of petroleum with sedimentary rocks.

Answer: First, this is an overstatement as oil has been located many times in non-sedimentary rocks, but sedimentary rocks contain trapping rocks or capstone rocks which are ideal for forming reservoir formations. This statement doesn't disprove abiotic origin as sediment forms layers of impermiable rocks that trap oil and gas as it rises from "source faults."

2) The close link between petroleum reservoirs and source rock as shown by biomarkers (the source rocks contain the same organic marker as the petroleum, essentially chemically fingerprinting the two).

Answer: As oil and gas rise from "source faults" at the bottom of the stratigraphic column, the capstone, or "roof rock" catches the oil, which then presses up against the shale or whichever capstone is in the particular geologic strata, running until it reaches final repose in the reservoir structure, so the oil uses the shale as a conduit. "Biomarkers" is false and has been demonstrated as such. Residue of the oil is left in the shale conduits on its way to final repose in oil trapping reservoir formations.

3) The consistent variation of biomarkers in petroleum in accordance with history of life on earth (biomarkers indicative of land plants are found only in Devonian and younger rocks, that formed by marine plantton only in Neoproterzoic and younger rocks, the oldest oils containing biomarkers of bacterial).

Answer: This is an overstatement of the evidence. Actually, there usually is a mix of bio-contaminents from all levels of the stratigraphic column from bedrock to the level the oil is trapped in. This statement is devoid of any acknowledgement that bio-contaminents are not proof that oil formed in the particular level in the stratigraphic column the oil was found in. Again, Dr. Clarke overstates "biomarkers" and their indicative value. He conflates so-called "biomarkers" and bio-contaniments; they are not the same.

3) Progessive destruction of oil when heated to over 100 degrees Celsius (precluding formation and/or migration at high temperatures as implied by the abiotic posulate).

Answer: Dr. Clarke is refering to the "oil window" and this idea has been thoroughly discredited by oil discoveries where the oil was hotter than 100 degrees Celsius. Abiotic oil is deep oil and numerous oil deposits have been found beyond 20,000 feet deep. This contention is the most discredited by actual oil discoveries.

5) The generation of petroleum from kerogen on heating in the laboratory (complete with biomarkers), as ssuggested by the biogenic theory.

Answer: Kerogen is a form of petroleum that has hardened with its volatiles escaped. Bitumen (what kerogen really is) has a unique property that when you heat it, it does crack into shorter hydrocarbon chains, but this in no way proves the bitumen is a precursor to oil, rather, it shows the opposite is true. Again, so-called "biomarkers" don't prove oil's origin -- its a redherring and following a redherring is something "fossil" theory has made a fine art out of doing.

6) The strong enrichment in C12 of petroleum indicative of biological fractionation (no inorganic process can cause anthing like fractionation of light carbon that is seen in petroleum).

Answer: This is false. J.F. Kenney has reported experiments that refute this contention convincingly. Passage through the stratigraphic column progessively strips out C13 from the hydrocarbon molecules.

7) The location of petroleum reservoirs down the hydraulic gradient from the source rocks in many cases (those which are not are in areas where there is clear evidence of post migration tectonism).

Answer: So what? So oil flows down the hydraulic gradient, abiotic theory does not preclude that at all, in fact, that's how oil migrates, but in no way does it prove or disprove either theory, since oil is abiotic and it has been observed doing what Clarke states. Again, another redherring.

8) The almost complete absence of significant petroleum in occurrences in igneous and metamorphic rocks.

Answer: This just the inverse of statement #1, so Clarke is already repeating statements. And it's an overstatement, just like the first time. Oil has been found in both igneous and metamorphic rocks. Sediment rock has many more trapping structures than the above so it's not surprising most oil is found in sedimentary trapping layers.

The evidence usually cited in favor of abiogenic petroleum can be better explained by the biogenic hypothsis, e.g.:

9) Rare traces of cooked pyrobitumens in igneous rock (better explained by reaction with rich country rocks, with which the pyrobitumens can usaully be tied).

Answer: How so Dr. Clarke? This statement is an assumption posing as a conclusion, there is no evidentiary basis for the statement. Actually, Clarke gives it away: "...the pyrobitumens can ususlly be tied." Obviously, in cases where there are no country rocks or sedimentary rocks, which by Clarkes admission there are, then there is no organic sediments, then no possibility of pyrobitumens (by "fossil" theory). But there are pyrobitumens present, thus conclusively proving abiotic origin for pyrobitumens.

10) Rare traces of cooked pyrobitumens in metamorphic rocks (better explained by metamorphism of residual hydrocarbons in the protolith).

Answer: Again, an assumption posing as a conclusion with no backup evidence. And worse, it actually proves abiotic theory, in that, if the pyrobitumen is "residual," how did it get there in the first place? By abiotic processes that's how.

11) The very rare occurrence of small hydrocarbon accumulations in igneous or metamorphic rocks (in every case these are adjacent to organic rich sedimentary rocks to which the hydrocarbons can be tied via biomarkers).

Answer: This is an understatement of the occurrence of hydrocarbons in igneous and metamorphic rock, similar to statements #1 and #8. There are numerous reports of hydrocarbons in igneous and metamorphic rocks. Why is Dr. Clarke repeating inacurrate statements? No, not in every case can the oil be tied to sedimentary rocks -- this is one of the big lies necessary for "fossil" theory, because once you allow the fact that there is oil in igneous or metamorphic rock without sedimentary rocks nearby, then the gig is up and it proves abiotic theory. But the inverse, is not true because you could have oil rise out of the "source fault" in the igneous or metamorphic rock and migrate into the sedimentary rock nearby. That would allow the miss-named biomarkers to be detected in both.

12) The presence of undoubted mantle derived gas (such as He and some CO2) in some natural gas (there is no reason why gas accumulation must be all from one source; given that some petroleum fields are mixed provenance it is inevitable that some mantle gas contamination of biogenic hydrocarbons will occure under some circumstances).

Answer: This is a begging statement posing as a conclusion. It would be possible, but that simply keeps "fossil" theory in the game. It's not a better explanation. it's a possible explanation. And, actually, if the He is significant, which it is in a couple of Oklahoma gas fields, it makes it that much more likely that it's more helium than the niggardly amount of mantle gas Clarke does allow for. It's also called "moving the goal posts, when Clarke has to, "okay, there is some mantle gas, but it incredibly rare -- no it's not.

13) The presence of traces of hydrocarbons in deep wells in crystalline rock (these can be formed by a range of processes, including metamorphic synthesis , by the Fischer-Tropsch reaction, of from residual matter as in 10).

Answer: Again, an understement of the facts, there are numerous examples of hydrocarbons in crystalline rocks. This is a repeat of statements #1, #8, and #11. This is not even a very cleaverly restated statement. Obviously, Clarke knows he's thin, and wants to be repetitive to sound more authoritative. But there are many examples of hydrocarbons in the crystalline rocks. And so what, there are other processes for petroleum creation, that's another redherring, as it doesn't exclude or offer a better explanation than abiotic processes, actually, those are also abiotic.

14) Traces of hydrocarbons gases in magma volatiles (in most cases magma ascend through sedimentary succession, any organic matter present will be terminally cracked and some wil be incorporated in the volatile phase; some Fischer-Tropsch synthesis can also occure).

Answer: As this website demonstrates, Clarke, again, understates how much hydrocarbons there are in and around volcanic activity, including 'solfataric' activity. Also, there are reports that volcanoes have released copious amounts of hydrocarbons from a single magna "throte" that had erupted many times before from the same "throte" that would have burned out any organic detritus long ago. The fact that Clarke is stating this obvious canard, means either, he doesn't know what he's talking about, or he's lying through his teeth, because these facts are powerful evidence for abiotic theory. Again, Fischer-Tropsch and other abiotic processes thow no doubt on abiotic theory as a whole.

16) Traces of hydrocarbons in hydrothermal fluids; these are also all compositionally consistent with derivation from either country rocks or Fischer-Tropsch synthesis.

Answer: Again, Clarke understates the role of mud volcanoes, and tar pits, and solfataric vents, and the documented evidence of large amounts of hydrocarbons being emitted from this type of crustal activity. Much more hydrocarbons are released, and for a longer amount of time, then a few country rocks or Fischer-Tropsch reactions would carry.

Dr. Clarke: "The geological evidence is utterly against the abiogenic postulate."

Oh, really!

What this "check list" showed was a constant attempt to obscure his statements with redherrings, or Clarke repeatedly misstating the facts, by either overstatement or understatement, whatever would help his side the most.

Some of his factual errors are so egregious, one can believe those statements were intentionally misleading.

And, this is a leader of "fossil" theory. What are the hacks like?

Anaconda said...


Much was made of the "check list" and that all 16 statements had to be answered to take abiotic oil seriously. Well, let's not count the fact that a number of the statements were repetitive. But, hey, that made it all that much easier to answer, and revealed the "final" check list as a paper tiger.

This writer suggests the real purpose of the check was to "bully" people who were inclined to believe abiotic oil.

Boy, when a theory has to engage in bullying tactics, to stay viable -- you know the theory wasn't all that viable to begin with.

Hmm... Dr. Clarke is an astrobiologist...he must really have his head up in the clouds.

Or if you think about, there's one other place...he's got his head up into...

OilIsMastery said...

The biogenic checklist is laughable. Absolute garbage.

Anaconda said...


My extreme apology. In reviewing the above statements and questions, it's readily apparent this writer made an omission in leaving out statement 15 and a corresponding answer for that statement. Please accept the apology for the omission. And here is #15 statement and my answer.

15) Traces of hydrocarbons gases at mid ocean ridges (such traces are not surprising given that the upper mantle has been contanimated with biogenic orgainic biogenic organic matter through several billion years of subduction, the answer to 14 may be applicable also).

Answer: The mid-ocean ridges are where magma is welling up from the mantle -- this molten rock would burn out any organic matter long before it resurfaced at the mid-ocean ridge. Dr. Clarke's answer pre-supposes that organic matter would survive, perhaps millions of years in a molten mantle, that seems unlikely (how far would these organics have to travel from a subduction zone out to the middle of the ocean in the mantle, again unlikely). More likely, these gases are primordial constituents of the mantle or it's possible Fischer-Tropsch synthesis occurs, but that does not disprove ultra-high heat and pressure formation of hydrocarbons.

Again, my apology for the omission, hopefully this supplemental is satisfactory.

Quantum_Flux said...

I suppose that photosynthesis of carbon and hydrogen on Mars would be different though, since Mars doesn't have much of a light filter.

Quantum_Flux said...

Other stars would have other evolutionary resonances based on the concentrations of different isotopes, different starlight, different light intensities, different seasonal variations, different angular momentums, and different gravitation fields.

Quantum_Flux said...

Hydrocarbons couldn't form at all around a star that has small quantities of hydrogen, C-12 stars.

Geologist said...

As said Sir Fred Hoyle:

"The suggestion that petroleum might have arisen from some transformation of squashed fish or biological detritus is surely the silliest notion to have been entertained by substantial numbers of persons over an extended period of time."