Re: Priority of Walther Loeb on `Miller' Spark Discharge Experiment

Stephen E. Jones (sejones@iinet.net.au)
Thu, 14 Oct 1999 19:02:02 +0800

Reflectorites

I got into trouble with Brian Harper a few years ago by claiming that
science's much-vaunted self-correction mechanism might not always work,
especially when it was too embarrassing for scientists to admit they had
been wrong for a long time on an important matter.

The case in point was Walther Loeb, who Yockey had pointed out in the
following Sci.bio.evolution post, carried out the first Miller-Urey type
spark discharge experiment in *1913*, ie. 40 years before Miller-Urey did
it in 1953.

Miller received a Nobel Prize for his work, but if Loeb did essentially the
same experiment 40 years before, and this is now widely known in the
origin-of-life field but is still being ignored, then it would tend to support
my claim.

According to Yockey, Miller was aware of Loeb's but misunderstood it due
to a mistranslation of the original German. At the time I wrote to the
Reflector: "It is difficult to believe that no German OOL scholar (there are
many) had not read Loeb's work and realised that Miller had got it wrong."

But I guess that was just possible that *everyone* had overlooked Miller's
mistranslation of Loeb's work until Yockey discovered it 43 years later in
1996. So my parting words on this thread to Brian in April 1996 were:

"But I will not totally rule out the possibility of cover-ups, because there
have been cover-ups in science in the past. I do find it hard to believe that a
German OOL researcher never noticed Loeb's actual words, but it is
possible. However, I will suspend judgement to see if in a reasonable
period of time (eg. a year?), Loeb will be given his rightful priority
(assuming Yockey is right)."

Well I had forgotten this and now it is more than *three* years since
Yockey broke the news to the biological community and Brian chastised
me for doubting science's self-correcting mechanism. I wonder whether
that self-correcting mechanism has worked and Loeb has at last been
exalted to his rightful place? Does anyone know what has happened
(or is happening) on this?

Steve

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Date: Tue, 20 Feb 1996 21:35:55 -0500
To: evolution@Calvin.EDU
From: bharper@magnus.acs.ohio-state.edu (Brian D. Harper)
Subject: Is it soup yet?

[...]

I found the following post from Hubert Yockey on sci.bio.evolution
and thought it might be of interest to the group.

If Yockey's analysis is correct, then it seems Loeb has been denied
his proper place in history due to a mis-translation of carbon
dioxide !

I would also be interested in opinions from geologists, geochemists,
paleontologists (I'm fishing for the appropriate "expert" category)
regarding lack of evidence for the soup in the 3.8 billion year
old Isua rocks. I did a little research on this awhile back and
found some references where "experts" were expecting to find geological
evidence for the soup.

Also, the meteorite bombardment seems significant to me. Earlier on,
these meteorite impacts were capable of sterilizing the entire planet
and even vaporizing the oceans. Their subsidence coincides (on a
geological time scale of course) with the first evidence of life.
This would indicate that the appearance of life was very rapid and
would also indicate that the "soup" (if there was one) should still
be around.

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================ begin post from Yockey; Sci.bio.evolution =============
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Subject: Priority of Walther Loeb on "Miller" Spark Discharge Experiment
(Chemical Evolution)
From: hpyockey@aol.com (HPYockey)
Date: 19 Feb 1996

Ian Vaithjilingam asked for details on how to do the spark discharge
experiments to generate amino acids in a presumed atmosphere of the early
Earth.

Thos who believe in the experiment are barking up the wrong tree.

The atmosphere of the early earth was not as Miller supposed. It was
neutral not reducing. There never was a primeval soup. See my comment
on this in "Information in bits and bytes" BioEssays v17 pp85-88 (1995)

I will send reprints if you send me your snail mail address.

The Miller-Urey experiment was not even original. The whole thing was
done by Walther Loeb in 1913 many years before Miller was born. Loeb's
publications make it clear that he was the first man to produce an amino
acid in the classic "possible prebiotic reducing (sic) atmosphere" of carbon
dioxide, ammonia and water by means of an electrical discharge.

The references to Walther Loeb's work are as follows: Ueber das Verhalten
des Formamids unter der Wirkung der stillen Entlandung. Ein Beitrag zur
Frage der Stickstoff-Assimilation Berichte der deutschen chemischen
Gesellschaft volume 46 (1913) pages 684-697

In English: The Effect of Silent Discharge on the Reactions of Formamide.
A Contribution to the Question of Nitrogen Assimilation published in the
Reports of the German Chemical Society (1913).

Upon reading Loeb's papers, I found that he knew exactly what he was
doing. The first sentence in this paper announced the purpose of the work
that led to the formation of glycine in the silent electric discharge: "The
question of natural nitrogen fixation is especially interesting in that it
presents the source of the first organic nitrogen containing product for the
formation of albumin bodies (that is, proteins)." Lob concludes his paper by
saying:

"There is no doubt that according to previous results the amino acid found
here is glycine.

Here succeeding for the first time, an amino acid has been produced
artificially from the input products of the natural synthesis, which in any
case, in the simplest phase, plays a role in the formation of natural protein
as the final products of the natural synthesis of carbonic acid [carbon
dioxide], ammonia and water without application of other materials, purely
through supplying a special energy form that remains in close connection
with the radiation."

How could Loeb say more clearly that he was working on a "prebiotic"
experiment to synthesize "prebiotic elements of protein"?

Stanley Miller is usually credited for being the first to find amino acids in a
"prebiotic experiment," but as he admitted in his 1955 paper, biochemists,
in particular Walther Loeb, had been exploiting the effects of electric
discharges in organic compounds, especially the fixation or assimilation of
nitrogen and carbon dioxide, long before he was born (ne 1930). Stanley
Miller, in his 1955 paper, "Production of some organic compounds under
possible primitive Earth conditions". Journal of the American Chemical
Society volume 77, pp2351-2361 (1955). cited the 1913 reference in which
Lob reported finding glycine in the silent discharge. He mistakenly stated
that Loeb used carbon monoxide in his silent electric discharge tube. If that
had that been the case it would give the impression that Loeb was not
interested in finding "prebiotic compounds" in the electric discharge. Upon
actually reading Loeb's papers in German, I found that he plainly had not
carried out his experiments in carbon monoxide but rather in damp carbon
dioxide and ammonia, the same environment often presumed (mistakenly)
by Miller and Urey and many others to have been that of the early Earth.
This false impression is due to a mistranslation and that may be why Loeb's
priority in this work has been ignored. The German word for carbon
monoxide is Kohlenoxyd, the word for carbon dioxide is Kohlensaeure
(literally, carbonic acid)-terms that are easy enough to tell apart.

As late as 1983 Miller and Schleschinger J. Mol. Evol. v19 pp376-382
quote Loeb's 1913 paper as using carbon monoxide not the correct carbon
dioxide.

Detailed references can be found to Loeb's work in "The Electrochemistry
of gases and other dielectrics by G. Glockler and S. C. Lind John Wiley
(New York) 1939.

This book mistranslates Kohlensaere as carbon monoxide. Perhaps this is
the source of Miller's mistranslation in Miller "Production of some organic
compounds under possible primitive Earth conditions". Journal of the
American Chemical Society volume 77, pp2351-2361 (1955).

Glockler and Lind is a compilation of abstracts of paper on
electrochemistry. It has a complete list of Loeb's papers and those of many
others on the question of the formation of organic materials under the silent
electrical discharge.

It is clear that Loeb thought his discovery of the formation, by means of
electrical energy, of biologically important substances such as glycine,
formic acid, formaldehyde, butyric acid, fatty acids and other compounds
was significant: See also Walther Loeb and A. Sato Zur Frage der
Elektrokultur I Mitteilung Die Einflussung von Enzymreaction durch die
stille Entlandung Biochemische Zeitschrift volume 69 pp1-35 (1915) He
and Sato had this to say:(my translation)

"On the ground of these relationships and practical knowledge one must
conclude further that electrical energy has an important meaning in life
reactions, that the knowledge of its role can be furthered only through a
long series of special undertakings.

The application of silent discharge is especially proper for such
undertakings on physical and chemical grounds. On physical grounds, while
under avoidance of higher temperature, the electrical energy unites with
ultraviolet ray exposure, especially as Warburg has shown previously. On
chemical grounds relatively strong chemical effects are experienced
(ausgeuebt).

And now to come to my own investigations, I wish to mention from the
earlier preparation of biologically important processes:
1. The assimilation of carbonic acid (H2CO3) higher than formaldehyde up
to glykolaldehyde from damp carbonic acid.
2. The synthesis of fatty acids that are brought up by the assimilation
of carbonic acid.
3. The synthesis of glycine from carbonic acid (H2CO3), water and ammonia
from the intervening steps of formamids, a reaction that can be the first
phase of nitrogen fixation on the way to protein.
4. The hydrolyzing of starch.
5. The deamination of glycine.

Walther Loeb, and others in his time, noted that they often found polymers
of various kinds in their discharge chambers, just as did Stanley Miller and
others many years later. Loeb reported in 1909 that he had frequently
smelled the unpleasant and characteristic odor of butyric acid during
investigations of the behavior of nitrogen in the presence of simple organic
compounds under the influence of the silent discharge. He thought that the
connection of the silent discharge reaction might be related to fermentation
processes.

Walther Loeb died after a brief illness on 3 February 1916, at the age of 44.

Miller has never given up the "primeval soup" although the atmosphere of
the early earth is now known not to have been reducing.

Would there not be geological evidence in rocks of 4 to 3. 8 billion years
old, if there had been such a soup? All methods of simulating the formation
of amino acids and other 'building blocks' leave a tarry polymeric material
as their most abundant product. Carbon that has once composed living
matter is slightly enriched in carbon 12. No chemical reaction, heat,
pressure or other treatment to which these ancient rocks may have been
subjected can change one of these isotopes to another. Thus the carbon
isotope ratio is a reliable and indestructible fingerprint to determine
whether carbonaceous material, including kerogen, came from living
organisms or by inorganic chemistry from a primordial carbon source.

Sedimentary rocks at Isua in Greenland have been dated at 3.8 billion years
ago, a time near the end of the late heavy bombardment. They do indeed
contain kerogen. Schidlowski (Nature 333, pp313-318; 1988) reported that
all carbon in these rocks divides distinctly into two groups, one high in
carbon 13 and one depleted in carbon 13 with respect to the isotope ratio
found in atmospheric carbon dioxide. The kerogen of the very old Isua
rocks is depleted in carbon 13. This is just what is expected if the kerogen
had been derived from cyanobacteria-like microorganisms capable of
photosynthesis of carbon dioxide and nitrogen by means of an enzyme
system to form living matter. Schopf Science 260 640-646 (1993), Moore
Nature 367 322-323 (1994)

According to the standard model of the origin of life, there are two paths
the carbon would follow in the primeval soup. The first is toward forming
the ancient protobiont, the remains of which would go to kerogen. The
second, and the much more abundant amount, is the tarry material
generated in all origin of life simulation experiments. No kerogen from the
tarry material left over from the generation of the 'building blocks' of life is
found. The significance of the very old kerogen in the Isua rocks in
Greenland is that there never was a primeval soup and that living matter
must have existed abundantly on Earth before 3.8 billion years ago.

Lazcano and Miller J. Mol. Evol v39 pp546-554 (1994) admitted that:
"Late accretion impacts may have killed off life on our planet as late as 3.8
billion years ago." The date of the Isua kerogen (3.8 billion years old)
shows that life was swarming at that time. There is simply not enough time
between the last sterilizing impact event for the generation of a primeval
soup and for the appearance of a proto biont that must have had the
enzymes capable of assimilating both carbon dioxide and nitrogen.

For further comment and references on the non existence of a primeval
soup in the oceans on the early Earth see Chapters 8, 9 and 10 in
Information Theory and Molecular Biology, Cambridge University Press
(1992); BioEssays v 85-88 (1995) and Journal of Theoretical Biology v176
349-355 (1995).

Best regards Hubert P. Yockey

Einstein: "God does not play craps with the world."
Bohr: "Einstein, stop telling God what to do!"
The gods actually did cast lots for the world as Homer tells us (Illiad )
See comment on page 88 of Information Theory and Molecular Biology
Cambridge University Press (1992)
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Stephen E. (Steve) Jones ,--_|\ Email: sejones@iinet.net.au
3 Hawker Avenue / Oz \ Web: http://www.iinet.net.au/~sejones
Warwick 6024 -> *_,--\_/ Phone: +61 8 9448 7439
Perth, Western Australia v "Test everything." (1 Thess. 5:21)
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