This will be the third of my in-depth responses to Steve's post; this one
deals with the environments in which proteinoids and microspheres are likely
to form.
> KB>To my knowledge, Fox never proposed this scenario, though others
> have.
>
> Then the problem seem's to be with Kevin's "knowledge".
>
Well, we cannot all be infallible like Steve. And notice how he takes an
admission that my knowledge may be incomplete and turns it into a handicap.
Before this gets too far out of hand, I need to explain some background here.
Part of the problem is that some prominent researchers, like Stanely Miller
and Leslie Orgel, misunderstood what Fox was actually proposing; another part
of the problem is that Fox did not try to correct their misunderstanding, but
simply addressed their scientific arguments based on their misunderstanding.
As such, later researchers, like Robert Shapiro, took Miller and Orgel's view
of the situation as factual and simply passed them along uncorrected. Also
as a result, other researchers who proposed volcanic rims claimed Fox as
their inspiration, despite the fact that he had made no specific mention of
volcanic rims in any of his scientific papers.
My claim is simply that Fox never **proposed** the idea of volcanic rims as
the best place for making proteinoids and microspheres. In none of his
scientific papers or books does he ever state anything like, "I propose that
the most likely location where proteinoids and their microspheres can be
formed is on the rim of volcanoes." What he actually proposed is broader,
more general than any one specific location. He did **discuss** volcanic
rims as possible locations for proteinoid microsphere formation, but only
**after** other researchers had suggested it, and only within the context of
whether such sites could form proteinoids and microspheres. He stated that
they could, and even did a few experiments to show that it was possible (as
well as address other, more general critiques), but for him volcanic rims
simply became another possible location within his broader proposal.
What Fox actually proposed was a plain of igneous rock the was geologically
active because of a geothermal source close to the surface. He also
suggested that such a plain should have frequent rains. Based on this rather
brief description, it is easy to see how people like Miller and Orgel could
mistakenly believe Fox was referring to volcanoes, especially if they believe
that volcanic rims were the only places where temperatures high enough could
be reached (to be discussed further later). Whether or not Fox had volcanoes
in mind can never be proven, since he wrote nothing specific, but there is
evidence that what he actually had in mind was a Yellowstone-type
environment. First of all, he makes reference to Yellowstone in his early
papers as the kind of area where proteinoids and microspheres could be
produced. Secondly, he was aware as early as 1953, before he had published
any paper on proteinoids, through the early work of Joseph Copeland, that a
Yellowstone-type environment was conducive to the formation of proteinoids
and microspheres. I find it highly unlikely that he would form this opinion,
abandon it briefly for a more problematic location, then pick it up again
shortly thereafter. It is more likely he had this idea in mind all along,
but his initial proposal was so general it allowed other researchers to fill
in gaps using their own biases.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
S.W. Fox (1988) The Emergence of Life, Basic Books.
S.W. Fox, et al. (1995) "Experimental Retracement of the Origins of a
Protocell" in C. Ponnamperuma and J. Chela-Flores, eds., Chemical Evolution:
Structure and Model of the First Cell, Kluwer Academic Publishers.
>
> According to
> Shapiro, Fox was indeed involved in such "volcano" experiments:
>
But being involved in experiments based on volcanic environments is not the
same thing as proposing volcanoes as the most likely place for proteinoid
microsphere formation. Fox's original proposal involved igneous rocks and
geoactive areas, which would undoubtedly include volcanoes, but Fox did not
specifically mention volcanoes or volcanic rims.
>
> "Professor Fox and his co-workers have been agile and flexible in
> attempting to meet such criticisms. Initially they suggested the rims of
> volcanoes as plausible sites where the necessary temperatures could
> be provided that were needed to form the proteinoids.
>
Again, Fox never proposed this idea originally in any of his papers or books;
he discussed it after others proposed it in his name, but never corrected
them. It was Miller and Orgel who proposed that volcanic rims were the only
places that were hot enough to make proteinoids. Fox refuted the idea that
volcanic rims were the **only** plausible location, but he didn't try to
correct their mistaken belief that that was what he was suggesting.
>
> Rain would
> subsequently remove them from the volcanoes and convert them to
> microspheres.
>
Rain did figure prominently in Fox's actual proposal. Fox's idea, however,
was that amino acids were formed in and on the rocks by any number of
gaseous, aqueous or solid phase prebiotic mechanisms, using geothermal heat
as the primary source of energy but augmented by electrical discharge and
ionizing radiation, and that the rain leached the amino acids and other
water-soluable organic molecules out or off of the rocks into pools on the
plain. When the pools dired up, the geothermal heat would copolymerize the
amino acids into proteinoids. When the rains returned and refilled the
pools, the proteinoids would form microspheres, incorporating whatever other
soluble organic material (lipids, saccharides, nucleotides, hydrocarbons,
etc.) were available. If the rains then washed these microspheres into
larger permanent pools, they could persist and even compete with one another
in a form of prebiotic evolution. Fox later amended this idea to take into
account Rohlfing's results showing that microspheres could be formed at
temperatures less than 100 C (see Re: God...sort of -- Yockey for details),
thereby augmenting -- or even replacing -- geothermal heat with solar heat.
Alternatively the amino acids could have been made in hot springs, and rains
could have caused the solution to overflow onto the plain into shallow pools
that again dried up when the rains ceased. After copolymerization, refilled
pools could overflow back into the hot springs, which could then flow into
cooler permanent pools fed by the springs.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
S.W. Fox (1988) The Emergence of Life, Basic Books.
S.W. Fox, et al. (1995) "Experimental Retracement of the Origins of a
Protocell" in C. Ponnamperuma and J. Chela-Flores, eds., Chemical Evolution:
Structure and Model of the First Cell, Kluwer Academic Publishers.
>
> To illustrate this concept, a sample of lava was
> collected at a volcanic site in Hawaii and brought to the laboratory of
> Professor Fox. The preparation of microspheres was then carried out
> within a depression of the lava sample. This scenario was subsequently
> extended to other locations." (Shapiro R., 1986, p197).
>
Shapiro has this backwards. Fox used the lava rocks to answer critiques that
claimed that thermal copolymerization in laboratory glassware was
unrealistic, and that a more realistic venue, like a hunk of lava rock, would
not produce proteinoids or microspheres. Fox demonstrated that proteinoids
could form on heated lava, then further demonstrated that these proteinoids
could be washed off by water and form microspheres. As such, it was meant to
vindicate his general proposal. It was only later that these results were
applied to the specific case of volcanic rims.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
S.W. Fox (1988) The Emergence of Life, Basic Books.
>
> KB>What he instead proposed was an environment similar to the
> >Yellowstone hot springs of today.
>
> That Fox also proposed "hot springs" does not mean he did not originally
> propose volcanoes.
>
No it doesn't, but since Fox did not propose volcanoes in his scientific
papers, since he mentioned Yellowstone Park as the kind of environment he was
proposing and since he knew about the potential of hot springs even before he
published any of his papers, I believe it is safe to conclude that he had hot
springs, and not volcanoes, in mind all along.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
S.W. Fox (1988) The Emergence of Life, Basic Books.
>
> Orgel also indicates that Fox originally proposed
> volcanos as the heat source since that was thought to be the only place on
> Earth where temperatures were high enough to polymerise amino acids:
>
In point of fact it was Orgel and Miller who believed that volcanoes were the
only available source of heat energy for abiogenesis, and so when Fox made
his general proposal, Miller and Orgel assumed he was talking about volcanoes
when he described a geoactive lava plain. Fox adequately rebuted this by
using hot springs as an alternative location.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
S.W. Fox (1988) The Emergence of Life, Basic Books.
S.W. Fox, et al. (1995) "Experimental Retracement of the Origins of a
Protocell" in C. Ponnamperuma and J. Chela-Flores, eds., Chemical Evolution:
Structure and Model of the First Cell, Kluwer Academic Publishers.
>
> "If a solution of amino acids is heated gently, water is driven off and a
> solid cake of organic material is left behind. On stronger heating,
chemically
> bound water is eliminated and, under certain circumstances, peptides are
> formed...However, the reaction does not occur at temperatures
> substantially below 130 degrees C.
>
At the time that Orgel wrote this that was believed to be true, but only
because no one had tested it experimentally. It wasn't proven false until
three years later (see Re: God...Sort of -- Yockey for details).
>
> The highest temperatures reached at the
> surface of the earth today, except in volcanoes, is close to 80 degrees C,
> and it seems unlikely that substantially higher temperatures occurred at
the
> surface of the primitive earth.
>
Based on what was believed to be true at the time, Orgel declares that such
temperatures could only be found on volcanoes.
>
> Thus the thermal polymerization of amino
> acids by direct heating could have occurred only in volcanoes.
>
Believing that only volcanoes could get hot enough to make proteinoids, he
concludes that volcanoes were the only places where proteinoids could form.
>
> Reasons for
> questioning that volcanoes were important for the origins of life have
been
> given already...However, this is an undecided issue and a number of
> authors, particularly the American scientist Dr. Sidney Fox, believe that
> volcanoes played a major role in the synthesis of organic polymers on the
> primitive earth." (Orgel L.E., "The Origins of Life", 1973, p139)
>
Finally, believing that volcanoes were the only places where proteinoids
could form, he declares that Fox must "believe that volcanoes played a major
role in the synthesis of organic polymers on the primitive earth" based on
Fox's general proposal, even though Fox did not specifically propose
volcanoes. Fox, however, was able to refute this by pointing out that even
today there are geoactive areas where the ground can get quite hot, even over
100 C; such areas were bound to be more numerous on the prebiotic Earth and
were bound to be hotter.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
S.W. Fox (1988) The Emergence of Life, Basic Books.
In conclusion, it seems far more likely that the idea that Fox proposed
volcanic rims as the most likely or only site for proteinoid formation is
based on the uncorrected opinions of Miller and Orgel being accepted as fact
by Shapiro, rather than on anything Fox himself actually proposed in his
scientific writings. It also seems most likely that Fox had a hot
spring-type environment like Yellowstone in mind all along; he just hadn't
described it explicitely in the beginning.
>
> KB>The springs would provide the water and other ingredients to create the
> >amino acids, and the underlying geothermal heat would provide the
> >energy necessary to dry-up isolated pools of water, then copolymerize
> >the anhydrous amino acids into proteinoids. Rain or overflow from a
nearby
> >spring would then rehydrate the proteinoids and cause them to form
> >microspheres. But this is by no means the only plausible scenario. All
> >that is really needed is periodic dehydration/rehydration and enough heat
> >to perform the copolymerization.
>
> Davis and Kenyon summarise the "Problems with Proteinoid Microspheres":
>
> "First, in his experiment Fox used mixtures containing only
protein-forming
> L- amino acids. Where on the primitive earth could such a mixture have
> occurred?
>
This has already been dealt with in more detail in "Re: God...Sort Of --
Yockey" and in "Re: God...Sort Of -- Protocell Characteristics". To
summarize briefly, proteinoids can be made from proteinous or nonproteinous
amino acids, or both, of either L- or D- configuration, or both, in the
presence of a wide variety of organic and inorganic contaminants. This poses
no problem for the primitive earth.
>
> We have already seen that thousands of interfering cross-
> reactions would have occurred in the soup, preventing the successful
> fulfillment of Assumption No. 3 of Oparin's hypothesis. These would have
> tied up protein-forming amino acids like Fox used.
>
Without knowing the details of these "interfering cross-reactions" it is
impossible to comment directly, but from the language of the statement
("would have occurred" rather than "does occur") it suggests that this
conclusion is based on speculation and not experiment. In other words,
neither the authors themselves nor anyone else has actually done any
experiments to test whether these cross-reactions would actually interfere
with proteinoid formation. The problem with this kind of critique -- one
that is based on theoretical grounds only -- is that all it does is call the
model into question. To actually disprove the model the theoretical basis of
the critique itself must be tested and verified by experiment, and there are
usually far more proposed critiques than tested critiques.
D.L. Rohlfing (1974) "Evolution of Models for Evolution" in K. Dose, S.W.
Fox, G.A. Deborin and T.E. Pavlovskaya, eds., The Origin of Life and
Evolutionary Biochemistry, Plenum Publishing.
Besides, the prebiotic soup is not the only method by which amino acids can
be made. Fox himself was able to make amino acids, including large amounts
of dicarboxylic amino acids, by heating a mixture of formaldehyde, water and
ammonia to 180 C in the presence of lava rock. The amino acids adhered to
the lava, and could either be washed off or left to form proteinoids, then
washed off. This kind of solid-phase reaction would not suffer from the
speculated problems of the prebiotic soup and it would produce large amounts
of the right amino acids in the exact place where they are needed to make
proteinoids.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
>
> Some of these
> substances would have combined directly with amino acids thus blocking
> the formation of proteinoids.
>
Again, this is speculation with no direct experimental support. Again, this
would not be problem in a solid-phase synthesis.
>
> For example, we have already seen how
> sugars react with amino acids to form the nonbiological compound known
> as melanoidin.
>
Mixtures of sugars and amino acids, when heated, still produce proteinoids,
so there is experimental evidence that demonstrates that this critique is
unfounded.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
>
> Because of such cross-reactions, which Oparin assumed did
> not occur, it is very unlikely that proteinoids could have formed under
> natural conditions on a primitive earth.
>
Again, more speculation with no direct experimental support. Again, this
would not be problem in a solid-phase synthesis.
>
> In short, many scientists agree that
> Fox's use of selected and purified amino acid mixtures isn't realistic.
>
But not for the reasons Davis and Kenyon suppose. Also, they do not object
to the experimental expedience of using purified amino acids. Finally, we
have experimental evidence that demonstrates that the amino acids do not need
to be pure, and that any mixture that contains glycine, aspartate, glutamate
or lysine will produce proteinoids.
>
> Second, there is disagreement about the proposed sequence of events
> which supposedly occurred near volcanoes. The required combination of
> high and low temperatures, with rainstorms occurring just at the right
time
> and place, seems unrealistically "choreographed" and highly improbable to
> many scientists.
>
Actually it doesn't, though it may seem improbable to Davis and Kenyon; as I
said before, this is not why most scientists consider proteinoids and
microspheres to be irrelevant. Volcanoes themselves go through periods of
high output and low output, so the volcanoes themselves can produce cycles of
high and low temperature. Besides which, rain can cool surface rock enough
to protect the newly formed structures, and it can remove them from the heat
source and transport them to safer areas where they can thrive.
As for "rainstorms occurring just at the right time and place", this is a
strawman view. The rains need only occur frequently enough over a wide
enough area to be effective; no "choreography" is needed. Here in Denver,
there is a period between mid-July and Mid-September when one can expect
rainstorms every afternoon and early evening. It doesn't happen every day in
all areas of MetroDenver, but it does happen often enough over a large enough
area that, statistically speaking, one can expect a rainstorm in Denver every
afternoon. If this were a geologically active prebiotic area, with the
mountains as active volcanoes, the general pattern one could predict would be
amino acid/proteinoid formation on the mountains in the morning, followed by
rains that would temporarily cool the igneous rocks, leach out the amino
acids/proteinoids and wash them down into pools on the plain. While it would
not happen everywhere everyday, it would happen somewhere most-days, and it
would happen often enough over a wide enough area that large amounts of amino
acids and proteinoids would be washed down the mountains onto the plain
virtually every day, statistically speaking. Thus it would only appear to be
"choreographed" from a statistical point of view.
>
> Even if proteinoids did form, the heat which formed them
> would also have destroyed them....
>
Incorrect. It only takes a couple of hours of heat to make proteinoids; it
takes many more to destroy them, so the process has an equilibrium that
favors formation over destruction.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
>
> ...or they would have broken down
> spontaneously before they could have played a role in the formation of
life.
>
Again, proteinoids are very stable. In the absence of bacteria or enzymes or
acid, polypeptides simply do not break down in water. As a protein chemist I
know this for a fact, and if anything proteinoids are even more stable than
modern proteins, not less. Proteinoids have been kept in sterile solutions
for up to six years with no significant loss due to hydrolysis. This is
simply no problem.
S.W. Fox and K. Dose (1977) Molecular Evolution and the Origin of Life,
Revised Edition, Marcel Dekker Publisher.
>
> Most important of all, even if these problems were solved, big differences
> exist between proteinoid microspheres and the very simplest living cells.
"
> (Davis P. & Kenyon D.H., "Of Pandas and People," 1993, p53).
>
This has already been dealt with in "Re: God...Sort Of -- Protocell
Characteristics". In brief, protocells display many, if not nearly all, the
important characteristics of modern cells.
In conclusion then, there really is no problem with a volcanic scenario for
the formation of proteinoid microsphere protocells.
>
> KO>As I pointed out earlier, this is not necessary. Simple evaporation
> >under a hot sun, such as you can find in any arid region nowadays,
> >would be sufficient.
>
> So we don't even need volcanos, or "hot springs"? We should be able to go
> and find naturally occurring proteinoids anywhere there is "Simple
> evaporation under a hot sun...such as" we "can find in any arid region
> nowadays"?
>
On the prebiotic earth, yes.
>
> Especially since they are supposed to be "living"? There should
> be *millions* of them, not only being spontaneously created new, but many
> more that are the *offspring* of all the originally created proteinoids
over
> the last 3.8 billion years.
>
It sounds like Steve is saying that we should be able to find proteinoid
microsphere protocells being made today. I cannot rule that out a priori,
but there are two reasons why that is highly unlikely. The first is that you
need a source of free amino acids, and there are no free amino acids in
nature, nor any process by which to make them. All amino acids in the
biosphere are tied up in proteins, and all proteins are tied up in organisms.
Secondly, the modern biosphere contains bacteria. Bacteria would not only
eat any free amino acids that might be available, but since proteinoid
microspheres are made of polypeptides, they make excellent bacteria food.
Purina Bacteria Chow. If you want to keep proteinoid microspheres in the lab
longer than a week, you have to use rigorously sterile conditions, or the
liberal use of antibiotics or respiratory toxins like sodium azide.
On the prebiotic earth there were no bacteria, so proteinoid microsphere
protocells could form anywhere where there was enough amino acids in an
enviroment that permitted cyclical dehydration/rehydration.
>
> And then why do we need Fox's high-tech laboratory experiments to produce
> proteinoids....
>
It ain't high tech. The method is so simple I can do it in my kitchen with
an oven, or, if I don't mind waiting three months, without an oven.
>
> ...if they are geologically and bichemically realistic and can be
> formed naturally anywhere there is "Simple evaporation under a hot sun,
> such as you can find in any arid region nowadays"?
>
Again, if Steve is asking why we cannot go to the Arizona desert and collect
protocells growing wild, the answer is simple: proteinoid microsphere
protocells make excellent bacteria kibble.
Kevin L. O'Brien