Journal of Molecular Evolution

https://doi.org/10.1007/s00239-018-9839-7

ORIGINAL ARTICLE

Mineral Grains, Dimples, and Hot Volcanic Organic Streams: Dynamic

Geological Backstage of Macromolecular Evolution
Nikolai E. Skoblikow1,2 · Andrei A. Zimin3

Received: 11 September 2017 / Accepted: 24 March 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
The hypothesis of hot volcanic organic stream as the most probable and geologically plausible environment for abiogenic
polycondensation is proposed. The primary synthesis of organic compounds is considered as result of an explosive vol-
canic (perhaps, meteorite-induced) eruption. The eruption was accompanied by a shock wave propagating in the primeval
atmosphere and resulting in the formation of hot cloud of simple organic compounds—aldehydes, alcohols, amines, amino
alcohols, nitriles, and amino acids—products, which are usually obtained under the artificial conditions in the spark-discharge
experiments. The subsequent cooling of the organic cloud resulted in a gradual condensation and a serial precipitation of
organic compounds (in order of decreasing boiling point values) into the liquid phase forming a hot, viscous and muddy
organic stream (named “lithorheos”). That stream—even if the time of its existence was short—is considered here as a geo-
logically plausible environment for abiogenic polycondensation. The substances successively prevailing in such a stream
were cyanamide, acetamide, formamide, glycolonitrile, acetonitrile. An important role was played by mineral (especially,
phosphate-containing) grains (named “lithosomes”), whose surface was modified with heterocyclic nitrogen compounds
synthesized in the course of eruption. When such grains got into hot organic streams, their surface catalytic centers (named
“lithozymes”) played a decisive role in the emergence, facilitation and maintenance of prebiotic reactions and key processes
characteristic of living systems. Owing to its cascade structure, the stream was a factor underlying the formation of mineral-
polymeric aggregates (named “lithocytes”) in the small natural streambed cavities (dimples)—as well as a factor of their
further spread within larger geological locations which played a role of chemo-ecological niches. All three main stages of
prebiotic evolution (primary organic synthesis, polycondensation, and formation of proto-cellular structures) are combined
within a common dynamic geological process. We suppose macromolecular evolution had an extremely fast, “flash” start:
the period from volcanic eruption to formation of lithocyte “populations” took not million years but just several tens of min-
utes. The scenario proposed can be verified experimentally with a three-module setup working with principles of dynamic
(flow) chemistry in its core element.

Keywords  Abiogenesis · Volcanism · Prebiotic chemistry · Flow chemistry · Translation

Introduction

An analysis of the problem of abiogenic polycondensation

* Nikolai E. Skoblikow
skoblikow@yandex.ru
1
Laboratory of Microbiology, Krasnodar Research Center
of Zootechny and Veterinary, 4 Pervomayskaya Street,
Znamenskiy Settlement, Krasnodar, Russia 350055
2
Medical Laboratory “CL”, 96 Moskovskaya Street,
Krasnodar, Russia 350000
3
Laboratory of Molecular Microbiology, Institute
of Biochemistry and Physiology of Microorganisms, 5
Prosp. Nauki, Pushchino, Moscow Region, Russia 142290
of monomers into polymers (e.g., amino acids into pep-
tides) inevitably comes to the problem of “water paradox”:
being the main product of polycondensation, water is, at
the same time, its inhibitor (Benner 2014). Hypotheses
dealing with the problem suggest different solutions to the
paradox: sorption by clay minerals (Paecht-Horowitz 1974),
dry-wet cycles (Commeyras et al. 2002; Ross and Deamer
2016), tidal cycles (Lathe 2003) etc. Despite the differences
between these solutions, their common point is that, one
way or another, water needs to be periodically removed from

13
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the reaction space of polycondensation. In contrast to this
viewpoint, we suggest a model of polycondensation under
special geological conditions, which are characterized by
the initial absence of liquid water, binding of the emerging
water by abiogenically synthesized organic water-binding
compounds and its continuous directed dynamic evacuation.
The natural events as resulting in that reproducible abiogenic
polycondensation as further resulting in extremely fast emer-
gence of first proto-cellular forms were considered as a part
of a common geological process.
Volcanogenic Synthesis of Primeval Organic
Compounds
Since the times of Miller’s experiments (Miller 1953), sci-
entists have established a great variety of ways, by which
organic compounds can be synthesized abiogenically in
the modeling conditions of the primeval Earth. In addition,
since the discovery of formaldehyde in the interstellar space
(Snyder et al. 1969), a large number of natural extraterres-
trial sources of abiogenic organic compounds (meteorites,
planets, interstellar space) have been revealed.
We consider abiogenic organic synthesis occurred in
the primeval atmosphere in the result of explosive volcanic
eruptions. Despite the differences in the views on the com-
position of atmosphere of the primeval Earth (Shapiro 1987;
Trail et al. 2011), we agree with the conclusion that “…
the volcanic apparatus experiment suggests that, even if the
overall atmosphere was not reducing, localized prebiotic
synthesis could have been effective” (Johnson et al. 2008).
The synthesis of primeval organics occurred locally, in the
atmospheric zone directly contacting the eruptive column
(i.e., in the shock-wave zone). The pressure in that zone was
a few times higher than the atmospheric one (whatever it
was at that time), and the temperature was in the range of
350–400 °C. We do not (and hardly will) possess convinc-
ing data on the differences of the composition of the erupted
gaseous products between ancient and modern volcanoes
(Sigurdsson et al. 1999). For this reason, we first and fore-
most consider the volcanic eruption as a high-energy geo-
logical event, resulting in: (1) an aerodynamic impact (shock
wave), with a sharp local jump of pressure and atmospheric
(as well as superficial) temperature; (2) the emission of large
quantities of incandescent mineral grains, whose total sur-
face served as a catalytic reaction area for the synthesis of
organic molecules; (3) the electric discharges caused by the
fast movement of charged mineral grains, leading to ioniza-
tion of erupted and atmospheric gases; (4) the rapid cooling
of peripheral zones of the eruption ash–gas column, prevent-
ing destruction of the synthesized organic molecules and
ensuring their fast removal from the reaction zone.
It is important to note that the erupted mineral grains
were very porous. Consequently, organic molecules could
13
Journal of Molecular Evolution
be synthesized inside those micro/nano-pores. Most of the
synthesized molecules would have been quickly desorpted
from the grain surface, forming a hot cloud of organic com-
pounds. Some of them, however (first of all the largest and
most complex ones, including various heterocycles), could
remain adsorbed in the micropores. Under extremely condi-
tions of shock-wave zone (abrupt changes of pressure and
temperature), those molecules could even be incorporated
into the surface layer of the crystal lattice of the mineral
grains. We consider these grains—the grains whose surface
was modified with relatively complex organic substances—
that played a key role in further evolutionary events.
The Composition of Volcanogenic Organic Cloud
and the Most Probable Primeval Organic Solvents
Scientists have identified complex organic compounds in
interstellar space (e.g., glycine, Kuan et al. 2003) and even
in protostar systems (Ligterink et al. 2017). The carbon-
rich meteorites can contain more complex substances, such
as hydroxy-, imino-, keto-, and amino acids (Cronin and
Pizzarello 1997; Pizzarello et al. 2001), nucleobases and
other N-heterocycles (Stoks and Schwartz 1982), as well as
substances of many other chemical classes. In the laboratory
experiments on abiogenic synthesis of organic compounds,
researchers obtained not only amino acids but also oligomers
of various (mainly hydrophobic) amino acids (e.g., Rodri-
guez-Garcia et al. 2015). There is a high probability that
all these compounds could be synthesized in the primeval
atmosphere within the suggested volcanic scenario.
If the described by us scenario happened on the primeval
Earth, the organic component of eruption clouds of ancient
volcanoes would be mainly represented by simple organic
substances (carboxylic acids, aldehydes, alcohols, amines,
nitriles) with a small number of atoms (5–10). At present,
there are about 20 of different schemes of abiogenic synthe-
sis of organic compounds in the laboratory setups, which
model, more or less successfully, various geological con-
ditions and processes of the primeval Earth (Rode 1999).
Substantial part of the products of various experiments on
abiogenic organic synthesis is represented not only by amino
acids but by simpler compounds, such as ethylamine, meth-
ylamine, ethanolamine, pyrrol, and others (Harada and Fox
1964; Bar-Nun et al. 1970; Khare and Sagan 1971; Hanic
et al. 2000; Parker et al. 2011).
The chemical composition of the volcanogenic organic
cloud could vary depending on the following conditions: (1)
the composition of the exhaled gases; (2) the composition of
the erupted ash; (3) the composition of the main rocks of the
streambed; (4) and climatic factors (temperature, precipita-
tion). The chemical composition of the organic cloud would
have been a mixture of simple aldehydes, alcohols, amines,
amino alcohols, nitriles, and amino acids—products often
Journal of Molecular Evolution
obtained under laboratory conditions in spark-discharge
experiments. Some of these compounds could serve as sol-
vents for amino acids and other monomers, allowing for
their polycondensation in the liquid phase. Such compounds
should possess the following characteristics: (1) simplic-
ity of chemical composition and confirmed possibility of
abiogenic synthesis; (2) a boiling point (­ Tboil) higher than
­Tboil of water; (3) a high water solubility and water binding
capacity and a high resistance to hydrolysis; (4) a certain
buffer capacity allowing the maintenance of a pH suitable
for polycondensation. We suppose the substances meeting
the specified requirements and successively prevailing in
organic streams were cyanamide, acetamide, formamide,
glycolonitrile, acetonitrile. The characterization of these
compounds is presented in Table 1.
Formation of Organic Stream
In spite of complex and variable composition of the primary
hot organic cloud, its subsequent cooling was resulting in a
gradual condensation and a serial precipitation of organic
compounds into the liquid phase in order of decreasing of
their boiling point values.
A significant amount of precipitation on the volcano’s
slopes near the eruption site would lead to the formation of
post-eruptive mudflows, which initially (in the temperature
range 400–100 °C) would were not aqueous but organic.
Today, post-eruptive mudflows (volcanic streams, volcanic
torrents or lahars) are a widespread volcanic phenomenon.
Lahars are mud-water streams, emerging right after the erup-
tion; they are formed in the modern conditions under the
effect of the same geological and physical factors.
It is important to note that, in spite of a significant con-
tent of vaporous water (first of all, a volcanic steam) in the
initial cloud, the content of water in the forming stream—
in the range of temperatures from ~ 400 to 100 °C—would
be extremely low. Moreover, after decreasing of the stream
temperature below 100 °C and substantial stream hydra-
tion, some part of water would be bound by hydrophilic
compounds (e.g., acetonitrile and methanol) which con-
densed upstream earlier. This concerns not only precipitated
water but also water produced in the further reactions of
polycondensation.
Table 1  Main primeval # Compound
organic solvents listed in the
order of their condensation 1 Cyanamide (carbamoni-
and precipitation from the trile)/Methanediimine
volcanogenic organic cloud
2 Acetamide
3 Formamide
4 Glycolonitrile
5 Acetonitrile
It is obvious that during flow, such a lahar-like stream
would undergo changes in its physical characteristics and
chemical composition. The composition of the stream
would change because of several factors, the most essen-
tial of which are the following: (1) continuous condensation
(due to cooling) and deposition of new compounds into the
liquid phase; (2) consumption of dissolved substances in
the ongoing chemical reactions; (3) sorption, aggregation,
and sedimentation of the heaviest, poorly soluble and high-
melting polymers; (4) continuous synthesis of water in the
polycondensation reactions (Fig. 1).
Role of Mineral Grains
Liquid organic compounds were not the only components
of the emerging stream. An essential component was min-
eral grains of various origins. There were volcanic ash par-
ticles (tephra) and debris of the main rocks, the particles
brought by winds and the meteorite fragments deposited
on the volcano slopes. All of them were washed off by the
organic volcanic flow. Notably that the particles of volcanic
ash are characterized by high porosity and decreased den-
sity resulting in significantly increased their mobility in the
stream—up to the possibility of flotation. All these grains
affected the stream rheology and played an important role
in the maintenance of chemical reactions going there. The
presence of a large quantity of mineral grains, as well as
a direct relationship between quite ephemeral existence of
the stream and volcanic activity of the lithosphere, allows
us to define such stream as lithorheos (ancient Greek: λίθος
[lithos] for “stone, mineral” and ρεύος [rheos] for “flowing,
stream”). We consider this hot, viscous and muddy organic
stream to be the most productive (for abiogenic polyconden-
sation) form of existence of Haldane’s “primordial soup”
(Haldane 1929).
Mineral grains played a few roles in the stream. First of
all, they were a factor of flow structuring, providing a dif-
ferent rheology in various loci of stream. Second, they could
provide a gel filtration-like selective sorption of organic
compounds from their mixture in the stream, described
earlier as “geochromatography” (Wing and Bada 1991;
Wächtershäuser 2006). Third, such grains (especially those
containing transition metals) could be as catalytic centers for
Formula N of atoms Tmelt (°C) Tboil (°C) ρ (g/mL)
H2NCN/HNCNH 5 44.0 260.0 1.28
H2NCOCH3 9 81.0 221.2 1.16
H2NCOH 6 2.5 210.0 1.13
HOCH2CN 7 − 72.0 99.6 1.10
CH3CN 6 − 44.0 81.6 0.79
13

Fig. 1  Gradient condensation of volcanogenic organic compounds
and formation of the organic volcanic stream. Different geological
locations of three main stages of prebiotic evolution (primary organic
synthesis, polycondensation, and formation of proto-cellular struc-
tures) combined within a common volcanogenic process. The erup-
tion volcanic cloud interacting with atmosphere is widening upwards.
The approximate boundaries of the zones of group precipitation of
organic compounds are indicated by isothermal lines. A group co-
condensation (because of azeotropic effect) of organic solvents is
shown. The streambed relief is shown in longitudinal section, with
no possible bifurcations or fusions. More detailed fate of mineral
grains and contents of streambed dimples are indicated: a formation
(in the shock-wave zone) of lithosomes as phosphate-containing min-
eral grains superficially modified with nucleobases (black dashes) by
local synthesis (upper row; “S” letter designed the synthesis) and/or
by adsorption (lower row); b lithotranslation of peptide (white spiral)
from dissolved amino acids (white dots) by lithosomes as described
in more details earlier (Skoblikow and Zimin 2016); c formation of
lithocyte with the range of identical/homological peptides, linear
nucleic acid (black hairpin) released from dissolved lithosome sur-
face, and membrane covering the filling dimple
a wide range of prebiotic reactions (Bernal 1951; Hazen and
Sverjensky 2010; Cleaves et al. 2012). The most important
role, however, was played by not purely inorganic grains
but by grains that were subjected to a superficial modifica-
tion—the incorporation of organic compounds (including
heterocycles) into surface layer in the course of eruption.
Modern biotechnology makes use of similar, artificially cre-
ated, organic-mineral complexes—ormosils, “organically
modified silicates” (Li et al. 1992). In our case, ormomins,
“organically modified minerals,” is probably more appropri-
ate. Under the conditions of catastrophic geological events
(explosive eruptions, meteorite impacts), complex organic
compounds (including nucleobases) could be synthesized
from simpler (mainly cyanic) substances on/in the sur-
face of mineral particles (Schwartz et al. 1982; Ferus et al.
2017), and their surface layer could then be immediately
modified by the organic compounds synthesized. The inclu-
sion of nucleobases into the bodies of meteorites seemed
13
Journal of Molecular Evolution
to occur according to the same scenario (Callahan et al.
2011). Apparently, heterocyclic compounds immobilized
in the surface layer were more effective catalysts compared
to pure inorganic clusters. We define such catalytic loci of
mineral grains as lithozymes (ancient Greek: λίθος [lithos]
for ‘‘stone, mineral” and ξύμη [zúmē] for “sourdough,
enzyme”), what emphasizes their function as primeval min-
eral-organic catalysts—precursors not only of enzymes but
ribozymes as well.
The most essential, however, could be the cases of
grain superficial modification by nucleobase pairs capable
of adsorbing the amino acids selectively, orienting them,
shielding their polar side chains (which would prevent an
interaction with each other), and facilitate the subsequent
abiogenic reproducible polycondensation of amino acids
into polypeptides. We define these processes as lithocoding
and lithotranslation as described in our previous article
(Skoblikow and Zimin 2016). Also we define such mineral-
organic grains as lithosomes (ancient Greek: λίθος [lithos]
for “stone, mineral” and σῶμα [sôma] for “body”), pointing
out their function as primeval mineral-organic pre-cellular
organelles. Lithosomes with embedded heterocycles can
be considered as lithozyme complexes, capable of catalyz-
ing various proto-metabolic reactions and cycles within an
extremely narrow space (on the scale of tens of nanometers).
A favorable factor for functioning of lithosomes in the
stream would have been their temporal retention in the natu-
ral cavities of the streambed.
Role of Relief of the Streambed
Post-eruptive streams appeared periodically after each
eruption characterized by a significant volume of produced
organics. This would have led to the erosion of volcanic
slopes. With the slopes being composed of different rocks,
their erosion should result in the formation of rough stre-
ambeds. Various streambed topological structures (cavities,
banks, rapids) played an important role in the local differen-
tiation of organic streams. Special attention should be paid
to small local cavities (hereinafter designated as dimples) up
to ~ 100 μm size, which appeared as a result of both local
changes in the stream rheology and kinetic impacts of falling
mineral fragments (of both volcanic and meteoritic genesis).
Those dimples were not mere debris collectors or kinetic
traps (Damer and Deamer 2015); being trapped there, grains
(as well as organic compounds) were selected, structured
and spatially organized. This was possible due to rheologi-
cal features of the stream, because of its laminar flow (with
light, fast-moving layers at the top and heavy, slow-moving
layers at the bottom), and the tendency of mineral grains
and macromolecular aggregates to the bottom accumulation.
When the flowing suspension was dense enough, the stre-
ambed dimples could become clogged with mineral debris
Journal of Molecular Evolution
with formation of microchannels in the sedimentary stratum.
The dimples with such contents can be viewed as microflu-
idic reactors which are characterized by special rheological
conditions of chemical reactions according to principles of
so-called “flow chemistry” (Wegner et al. 2011). It is these
conditions that we consider optimal for the reactions of abio-
genic polycondensation of amino acids.
Synthesis of Peptides and Lithotranslation
in the Hot Organic Stream
By now, researchers have described many ways of abiogenic
peptide synthesis (Ponnamperuma 1965; Paecht-Horowitz
1974; Lahav et al. 1978; Ferris et al. 1996). Furthermore,
various geological locations have been suggested as a suit-
able environment for mineral-mediated amino acid polycon-
densation (Ferris et al. 1996). The main distinctive feature
of our scenario is the consideration of hot organic stream
as the most plausible geological environment for reproduc-
ible (code-based) prebiotic synthesis of peptides. Deposition
of abiogenically synthesized amino acids into a hot flowing
organic solvent is a factor providing for: (1) dissolution of
amino acids (transfer into the liquid phase); (2) removal of
water by organic condensing/dehydrating agents, e.g., by
dicyandiamide (Steinman et al. 1965) in the course of poly-
condensation; (3) possible further modification of amino
acid side chains after polycondensation of amino acids into
peptides.
These conditions do not rule out—quite the contrary,
they imply—the possibility of formation of ultrameric (not
linear polymeric) proteinoids (Fox et al. 1959). Nor do they
exclude the possibility of an initial direct abiogenic synthesis
of polyamide backbone of polypeptide chains from aminom-
alonitrile molecules, which was also a product of primary
volcanic synthesis, with the subsequent attachment of side
chains (Schwartz et al. 1984; Matthews 2000). However, the
only mechanism that would ensure reproducible synthesis of
large quantities of linear peptides with the same (or similar)
sequence was the lithosome-driven lithotranslation.
The dimples containing translating lithosomes could
probably produce (and, with local sorption, accumulate)
large quantities of peptides of a certain, relatively nar-
row, spectrum. That would enable to differ the dimples by
(macro)molecular specificity. If the identical macromol-
ecules were retained in the places of their local production,
they would have formed growing clusters. The ability of
proteins to self-organize and self-assemble into more com-
plex structures, consisting of a multitude of identical pro-
tein units, is well known (Villar et al. 2009; Ahnert et al.
2015; McManus et al. 2016). Assembly of viral capsids and
various metabolosomes are the bright examples of such phe-
nomenon. It seems likely that the abilities of peptides to self-
organize and self-assemble into peptide complexes already
manifested themselves during the time of the primeval Earth.
Spreading downstream and interacting with each other, these
complexes could give form an increasingly larger macromo-
lecular aggregates. Synthesis, retention, accumulation, and
consolidation of the settling mineral grains, organic-mineral
complexes and macromolecular aggregates in the streambed
dimples were, probably, widespread processes during the
lifetime of such a stream. As a result, the contents of the
dimples would have reached a certain density leading to for-
mation of relatively isolated and structured mineral-poly-
meric aggregates. We consider that the described mechanism
of aggregate formation underlay the emergence of stable
complex macromolecular structures, evolutionary precur-
sors of cytoplasm and/or organelles of first cells, which were
hypothesized by many authors (e.g., “composomes” (Segré
et al. 2000; Norris et al. 2014), “polymerosomes” (Spinler
et al. 2013), and aggregates of various “oligomer worlds”).
It is these dense gel-like aggregates that would have mani-
fested, under the external influence of the stream, one of
the most unique features of the cytoplasm of living cells:
macromolecular crowding (Zimmerman and Trach 1988).
As for the streambed dimples, which were described earlier
by Wächtershäuser (2006) in a similar quality of “embryonic
caverns,” they played the role of mineral wombs for such
macromolecular “embryos.”
The cascade downstream arrangement of dimples was the
structural basis for a naturally formed organic-based ecologi-
cal (chemo-ecological) hierarchy. Apparently, macromole-
cules (especially, peptides, and proteinoids) and macromo-
lecular complexes synthesized in the upstream dimples were
catalysts themselves and, perhaps, folding-assisting agents
towards molecules accumulating in the downstream dimples.
In some particularly successful cases, aggregates of peptides
and nucleic acids could play the main role in the organiza-
tion of the functional core of the ancient ribosome (Skob-
likow and Zimin 2015). Thus, this hot organic stream with
a complex streambed relief became the real geochemical
conveyer of organic synthesis and the main geological driv-
ing force for further (macro)molecular cooperation (Higgs
and Lehman 2015).
Origin of Linear Nucleic Acids
Polypeptides would not have been the only polymers abio-
genically synthesized in lithorhei in the course of polycon-
densation reactions. In the case of phosphate-based litho-
somes modified with nucleobases, there was a possibility of
formation of linear molecules of nucleic acids in the course
of dissolution of the surface layer of the mineral grain crys-
tal lattice (Skoblikow and Zimin 2016). We, therefore, hold
the consideration that phosphate-containing (but not pure
silicate) minerals of volcanic origin played an exclusive role
in the discussed scenario—in agreement with the thesis that
13

“life is basically organized around phosphorus” (de Duve
1991; Rauchfuss 2008). The transformation of the crystal
lattice of insoluble phosphate mineral (apatite) into phos-
phate inter-nucleotide bridges of linear nucleic acid mole-
cules might have occurred in the course of process similar to
that described by Keefe and Miller (1996). It is noteworthy
that the organic agents (e.g., HSCN, HCOOH) that, accord-
ing to the scheme proposed, provided for the conversion of
apatite into soluble phosphates could have a constant and
productive source exactly within our scenario.
One should also not forget that nucleobases immobilized
on the surface of lithosomes could played a non-coding
role initially. They might not only sorb amino acids—they
might interact with similar mineral grains modified with
much larger polar compounds. With the sufficient increase
of the number of interactions, the grains could attach and
accrete to each other. The affinity binding of linear nucleic
acids onto apatite crystals is established and used in modern
biomedicine (Okazaki et al. 2001). Perhaps, the non-infor-
mational role of externalized chromatin (“NET formation”
and “NETosis”—the formation of extracellular networks
from DNA fibers and some proteins for trapping of pathogen
bacteria) of neutrophil granulocytes of modern multicellu-
lar organisms (Brinkmann et al. 2004; Yousefi and Simon
2016) is a manifestation of the relict polymer-corpuscular
interaction.
Formation of Microvesicles
If the conditions of the primeval Earth enabled abiogenic
synthesis of hydrocarbons and fatty acids (Peretó et  al.
2004; Proskurowski et al. 2008), the substantial hydration
of the stream—which occurred after decreasing of its tem-
perature to below 100 °C—could result in the accumula-
tion of the non-polar compounds at the stream surface layer
and the subsequent formation of films. In the ponds, which
should form in large hollows of the Earth’s surface, such
films would stick to pond edges—first of all, edges near the
outfalls of the inflowing streams (including volcanic). In
that case, macromolecular and organic-mineral aggregates
carried by the streams into the pond (already mainly aque-
ous and cooled to T < 100 °C—possibly, a Darwin’s “small
warm pond”) could be encapsulated in hydrophobic film-
based envelopes, preventing dissolution and disintegration
of amphiphilic aggregates in water. Most of abiogenesis
scenarios consider formation of such bubbles encapsulating
relatively mobile polymeric aggregates and separating them
from the aqueous environment with a hydrophobic barrier
as a necessary stage in the origin of life. However, despite
the obvious progress in laboratory studies of artificial con-
structs of this type (Adamala et al. 2016), the question about
mechanisms of their formation under prebiotic conditions
is still open.
13
Journal of Molecular Evolution
We think that the hypothesis of volcanic organic stream
is based on the most diverse combination of simultaneously
acting factors facilitating and accelerating formation of poly-
meric microvesicles in the hydrating stream: (1) swirling of
the stream because of relief irregularities; (2) fluctuations of
the streambed temperature (especially near fumaroles sur-
rounding the main crater) leading to local boiling up; (3)
fall of volcanic ash after the primary eruption able to cause
cavitation and formation of bubbles and films already in the
colloidal environment; (4) continuing seismic aftershocks.
Outpouring of the stream on the surface of the collector
pond could give another benefit, owing to the intermixing
of layers, splattering, and formation of bubbles (up to the
formation of prebiotic “foam”). The process would go much
faster and more productively in comparison to the cases
when bubbles were formed on the surface of large water
bodies under the effect of waves or some other, rarer, events.
We consider that the most perspective, from the evolution-
ary viewpoint, process was the formation of bubbles encap-
sulating not only dissolved macromolecules but also more
complex aggregates washed out from the streambed dimples.
Formation of Lithocytes
Formation of films from the compounds poorly dissolvable
in water could occur not only on the surface of hydrating
stream and collector pond but also at the phase boundary
within the stream flow: on the surface of aggregates accu-
mulating in the streambed dimples. The process could be
accelerated in the course of cooling of the organic cloud,
translocation of the 100 °C front closer to the volcano and
precipitation of water in the upstream regions—in other
words, at an earlier and sharply increased hydration of the
stream. Segregation of mineral-polymer aggregates retained
in the streambed dimples from the aqueous environment by
a membrane-like barrier was what we consider to be the
emergence of first cellular forms. We define such forms as
lithocytes (ancient Greek: λίθος [lithos] for “stone, mineral”
and κύτος [kytos] for “hollow, cell”), emphasizing the pre-
vailing role of the mineral component both in the function-
ing of such forms and in the nature of their outer boundaries.
Formation of earliest (proto)cellular structures in inorganic
compartments has already been discussed by other authors
(see, for example, Smith et al. 1999: “the first cell wall might
have been an internal mineral surface”). However, the mod-
els that have been suggested so far do not consider a scenario
of multifactorial rheology-dependent formation of the com-
plex contents of such compartments during very short time.
The mode of interaction of such immobilized proto-cel-
lular structures with the environment has been characterized
by Cavalier-Smith (2001) as “a primitive proto-ecology of
molecular scavenging.” Basically, it was consumption of
organic compounds and aggregates which were precipitated
Journal of Molecular Evolution
from the atmosphere and brought by a stream. However, a
possible (and even ordinary) events were the cases when
densely compacted mineral-polymer aggregates periodically
left their “maternal” dimple—as a result of washing out (if
the flow became faster) and/or of shaking out by seismic
impacts (perhaps, followed by the destruction of the dim-
ples). In that case, the stream could be not only a factor
of lithocyte formation but could also be an ecological fac-
tor of dissemination of mobilized lithocytes within much
larger geological locations, which could then be considered
a kind of chemo-ecological niches. With the environmental
conditions changing, there would have been some sort of
interaction between the immobilized lithocytes of different
(geo)chemical nature—in the form of association or even
incorporation. This fast (within several minutes) change of
chemo-ecological niches (especially, upon fusion of differ-
ent lithorhei) was a more powerful factor for selection and
early molecular evolution than any changes of parameters
in situ. Perhaps, the fast dynamics of these described events
can be an explanation for the fact that the age of discover-
ing most ancient cellular forms has increasing lately from
3.465 billion years (Schopf and Packer 1987) to more than
3.700 billion years (Nutman et al. 2016).
Further Fates of Lithocytes
It is important to keep in mind that volcanic streams are
quite ephemeral: they exist only for a short time (from sev-
eral minutes to a few hours). With a stream disappearing and
solidification of high-melting compounds at the streambed,
the further fate of lithocytes—both immobilized and freely
moved in the liquid phase—was primarily determined by the
temperature of environment, which resulted in either drying
or freezing of the major part of bottom contents.
In case of drying, the stream was gradually condensed to
consistence of a very dense suspension or even a paste. With
a long rainless period after the eruption and a high tem-
perature (above 100–200 °C), the stream would dry up com-
pletely and turn into “asphalt” (Benner et al. 2012). Such a
scenario could explain the granular structure of kerogens,
precursors of liquid oil, within the hypotheses of abiogenic
origin of hydrocarbons (Glasby 2006).
Nevertheless, high concentrations of organic compounds
(including polymers) could enable lithocytes to retain, dur-
ing short inter-eruptive intervals, the most low-boiling sub-
stances and some amount of water in the state of a dense
crust-covered gel—as described, for example, by Damer
(2016). We define this special state (phase of existence) of
lithocyte as cryptocyte (ancient Greek: κρυπτή [kruptē] for
“crypt, vault, secret chamber” and κύτος [kytos] for “hol-
low, cell”), pointing out its temporal structural organization
as a form which not only was containing minerals and was
protected with mineral walls but was also literally “buried”
under a layer of mineral grains. Under conditions of prime-
val Earth, the repeating eruptions would cause new “organic-
water rains,” filling in the “old” streambeds and reactivating
the cryptocytes. Being reactivated, the cryptocytes could
again become the main microreactors of primary prebiotic
condensation.
High concentrations of organic compounds also allowed
lithocytes (of course, the most successful ones) to retain
their structure when the stream or collector pond froze (at
T < 0 °C). It is noteworthy that such conditions are even
considered favorable for non-enzymatic polymerization of
activated RNA monomers (Monnard et al. 2002). Thus, the
chemical features of xero- and cryoprotection taking place
in modern living systems could be explained within our sce-
nario not as late evolutionary gains of living cells but as a
relict process, which reflects the earliest stages of evolution
of the organic (but still not biological) world.
It is clear that the fate of the majority of cryptocytes was
a “biological dead end.” Yet even the slightest non-zero pos-
sibility of preservation of some (probably, single), organic-
mineral aggregates (the most successful and structured ones,
able to reproductively synthesize peptides) would be enough
for their future evolution in more favorable environment—
evolution that would result in the emergence of more perfect
cellular structures characterized by autonomous homeosta-
sis, relatively stationary metabolic cycles and a genome
which could be replicated with a high degree of accuracy.
We suppose the areas near the outfalls of volcanic streams
as the most favorable locations for the search for molecular
fossils and traces of the most complex prebiotic evolution
on other planets (Fig. 2).
Combining of Three Different Geological Locations
Within Common Volcanogenic Process
Almost all the concepts of prebiotic evolution can agree that
“prebiotic chemistry is customarily divided into different
stages corresponding to an increasing degree of complexity
of the entities involved: (1) the synthesis of building blocks
(amino acids, nucleic bases, nucleosides, nucleotides...); (2)
the formation of polymers (nucleic acids, peptides); (3) the
emergence of supramolecular architectures including the
formation of the membrane and hence of individual cells”
(Pascal et al. 2006). The number of stages can be signifi-
cantly increased by dividing these three main stages into
smaller ones, but hardly can be decreasing since all the main
stages were different by their environmental conditions.
These differences were so essential that these three stages
should have passed in three different geological locations,
which were drastically differed in their physical–chemical
conditions but were combined within a common geological
process (Table 2).
13
 Journal of Molecular Evolution

Discussion

Advantages of Volcanogenic Synthesis of Primeval

Organic Compounds

Among many possible scenarios of abiogenic synthesis of

Fig. 2  Liquidogenic geological structures of Martian Ceraunis Tho-
lus. Non-terrestrial geological structures which presumably par-
ticipated in the volcanic scenario of prebiotic evolution in the region
of the extinct Martian volcano Ceraunis Tholus are indicated: a
the region of main crater/caldera; b canyons and valleys—dry stre-
ambeds; c collector Rahe Crater. Perhaps, these structures were
zones of primary organic synthesis, polycondensation, and formation
of macromolecular aggregates respectively. These are not the only
Martian structures of this type but they are, probably, the most illus-
trative. The most perspective region, in our opinion, for the search of
traces of complex prebiotic evolution is marked by a triple-line white
circle
primeval organic compounds, we give preference to vol-
canic and similar to them meteorite scenarios. In contrast
to “hydrothermal vent” scenarios, the synthesis of organic
compounds upon catastrophic atmospheric events would
have the following distinctions: (1) an extremely high ener-
getics of the event; (2) an available source of nitrogen and
N-containing compounds.
If volcanic eruption is compared to meteorite bom-
bardment, the former appears more plausible in respect to
organic synthesis for the following reasons: (1) relatively
long and regular local emissions; (2) lightning associated
with the plume (spark discharges); (3) larger volumes of
products; (4) porosity of the emerging mineral grains, result-
ing in a their larger surface area and their higher mobility
in the stream; (5) possible presence of associated nuclear
geysers, which could play an important role in the prebiotic
energetics (Ebisuzaki and Maruyama 2017).
An optimal course of events would be the combined sce-
nario of meteorite-induced eruption, in which “eruptions
were triggered by bombardment of the still young Earth’s
crust by heavenly bodies” (Basiuk and Navarro-Gonzalez
1996).
A high probability of the volcanic scenario is evidenced
by the following facts: (1) successful modeling of organic

Table 2  Three main stages of prebiotic evolution, taking place in three different geological locations within a common volcanogenic process

Stage 1. Primary organic synthesis Stage 2. Polycondensation and Stage 3. Formation of macromo-
formation of polymers lecular complexes and superstruc-
tures

Geological location Eruption column/cloud boundary Volcanic stream Collector pond

Dynamics of the system
Temperature (°C)
Content, aggregate state and main
role of water
Characteristics of the disperse
system
Approximate number of atoms
of the synthesized organic
molecules
Synthesis of polymers
Extremely high (gases under pres-
sure, shock wave, burning hot
ash, discharges)
> 280–300
Significant (~ 50%)
Vaporous
Reagent
Smoke (solid/gaseous), aerosol:
solid ash particles suspended in a organo(lyo)sol with amphiphilic sol with a hydrophilic solvent
gaseous phase
5–20
Almost absent; if present, then
direct backbone-modifying
(bypassing a monomer stage)
High (a swirling flowing of hot Moderate–low (Darwin’s “warm
muddy stream) little pond”)
280–100 < 100–80
Almost absent (traces because of High (> 90%)
azeotropic effect)
– Liquid
– Solvent (till the possible further
freezing)
Suspension (solid/liquid), Colloidal solution, hydro(lyo)
solvents; gel aggregates (water); foam (gaseous/liquid)
20–250 > 250
Mineral-dependent (including Polymer-dependent (by catalytic
lithotranslation) peptides and ribozymes)

13
Journal of Molecular Evolution
synthesis upon various manifestations of volcanism: exha-
lations (Fox and Harada 1961; Harada and Fox 1964) and
eruptions themselves (Lavrentiev et al. 1984); (2) discovery
of organic compounds among the products of modern vol-
canism (Markhinin and Podkletnov 1977); (3) data on the
biochemical composition of the most ancient cellular cyto-
plasms, indicating their volcanogenic nature (Mulkidjanian
et al. 2012).
We also do not rule out other possible ways of primary
abiogenic synthesis, which could make a contribution to the
common pool of ancient organics.
Organic Solvents
One of the ways to solve “water paradox” is to consider an
organic substance rather than water as the main prebiotic
solvent. The most studied and suitable candidate for the role
of such solvent is formamide (Saladino et al. 2006, 2012).
Some researchers, however, have doubts that formamide is
“a geochemically plausible prebiotic solvent” (Bada et al.
2016). Indeed, in regard to a number of features, other com-
pounds appear to be more preferable. For example, cyana-
mide is a simpler and “easier-to-make” molecule (5 atoms
vs. 6). Acetamide, in its turn, is much more thermostable:
it practically does not decompose at the point of its ­Tboil
(221.5 °C) (Emons et al. 1986). In comparison, formamide
decomposes to CO and ­NH3 at the atmospheric pressure
and temperatures above 160 °C and transforms into ammo-
nium formate ­(HCOONH4) in the presence of water. Some
researchers give preferences to acetonitrile (Adam et al.
2017) or hydroxyacetonitrile (glycolonitrile) (Ebisuzaki and
Maruyama 2017), which form as a result of the activity of
natural nuclear reactors.
We think that establishing “the most suitable” solvent
only makes sense if one considers the conditions and mecha-
nisms of its synthesis in the context of the whole system
of interconnected synthetic reactions leading to the forma-
tion of both the solvent and the dissolved substances. In
our hypothesis, which implies simultaneous synthesis of
dozens of different organic compounds, we do not single
out any substance as the “most plausible prebiotic solvent.”
Instead, we consider a mixture of various organic solvents—
a dynamic mixture whose composition was sequentially
changing in the course of synthetic processes (Table 1).
We also suppose that compounds not included in the table
(succinimide, succinonitrile, imidazole, pyrrolidone, malo-
nonitrile, carbamide (urea), ethanolamine, glyceraldehyde,
glycolaldehyde, pyrrole, acetic acid, butyronitrile, formic
acid, propionitrile, oxopropionitrile, ethanol, acrylonitrile,
dicyanoacetylene, methanol, aminoacetonitrile, hydroxy-
lamine, acetone, acetaldehyde, cyanoacetylene, ethylamine,
formaldehyde—listed in order of descending of ­Tboil) was
functioned as important additional solvents in the primordial
organic mixture. Many of those compounds found their place
as metabolites and osmo-/xero-/cryoprotectants in the mod-
ern living systems.
Streams and Dynamic (Flow) Chemistry
The importance of terrestrial (continental) prebiotic flow
systems in the origin-of-life studies has only been acknowl-
edged recently (Wächtershäuser 2006; Mulkidjanian et al.
2012; Patel et al. 2015), and only single of them consider
streams as important independent geo-locations for prebi-
otic synthesis (Sutherland 2016). They also analyzed some
key aspects of the problem, such as the prebiotic role of the
main rocks of the streambed and proto-ecological interac-
tions upon the fusion of different streams. Essential differ-
ences of our model are (1) assumption of the initially non-
aqueous nature of the stream; (2) thesis about an gradual
change of the stream temperature, density and chemical
composition; (3) consideration of the role of the streambed
morphology; (4) analysis of the role of mineral grains and
mineral-organic aggregates in the formation of polymers
and complex organelle-like structures; (5) general adaption
of the model to volcanic, rather than meteorite, scenario.
The concepts that recognize the important role of prebiotic
streams in the origin of life are, in our opinion, very perspec-
tive and should be developed further. They enable research-
ers to operate with various “dehydration–hydration cycles”
and other models with less intensive dynamics. There is no
doubt that prebiotic evolution occurred under such geologi-
cal conditions as well. However, it must have been much
less productive in comparison with the processes described
by our model.
Taking a step further, we also consider that biological
systems are partially conserving and reproducing—in their
most important functional structures—not only the chemi-
cal/mineral composition, reflecting the location of their ori-
gin (e.g., Fe–S clusters, phosphate granules), but also the
geological processes and phenomena that gave rise to those
systems. If that is the case, many biological processes related
to a directed flow of molecules and cells—from translation
and microfluidics in biofilms to peristalsis and blood circula-
tion in multicellular organisms—reproduce, in a sense, the
dynamic mode of the ancient organic streams.
Ways for Experimental Confirmation
An important feature of the hypothesis is the possibility of
its experimental verification. We consider it is possible and
important to design and construct the three-module setup,
which would combine all three major geological locations
of prebiotic evolution within a common dynamic geologi-
cal process. Such a system should include the following:
(1) a Miller-type chamber simulating the primary organic
13

synthesis under the conditions of volcanic cloud—with the
mandatory use of not only a gaseous but a fine-dispersed
mineral phase as well; (2) a cascade-flow module working
with principles of dynamic (flow) chemistry for modeling
the hot organic cascade flow with a complex streambed
relief; (3) a collector basin making it possible to follow the
fate of mineral-organic aggregates in a cooled hydrated
environment. We consider that experiments conducted in
such cascade-flow system would allow obtaining the answers
to many questions of prebiotic chemistry.
Conclusion
In contrast to majority of models of abiogenic synthesis of
organic polymers, we put forward a model of polycondensa-
tion in the hot (T > 100 °C) organic stream formed by con-
densed products of primary volcanogenic synthesis. Such a
stream is characterized by: (1) an initial absence (or a negli-
gible content) of liquid water; (2) a binding of the emerging
water by abiogenically synthesized organic water-binding
substances; (3) a continuous directed dynamic evacuation
of liquid water. The quick replacement of geological loca-
tions forms a geochemical cascade as the main space for
fast prebiotic evolution. The suggested cascade-flow model
combines the primary organic synthesis, polycondensation
of monomers and complexation of macromolecules within
a common geological scenario, making it possible to simul-
taneously resolve the following problems: (1) combining of
three topologically decoupled geological locations of main
three stages of prebiotic evolution within a common volca-
nogenic process; (2) nature and origin of the main solvents
at different stages of prebiotic evolutions and the mechanism
of their replacement; (3) a phased transition from the “hot
start” of chemical evolution in eruptive cloud and primeval
organic solvents till the beginning of the earliest biological
evolution in the cooled liquid aqueous environment; (4) ori-
gin, micro-architecture and functioning of organic-mineral
structures as proto-organelles (probably, predecessors of
acidocalcisomes and ribosomes); (5) continuous and fast
prebiotic synthesis (including reproductive, i.e., code-based,
synthesis) of substantial amounts of oligopeptides in the
waterless organic environment; (6) formation of macromo-
lecular complexes in a very short (comparatively to other
models) time; (7) consideration of suitable solutes func-
tioning under extremal conditions as low-molecular marker
relicts of the ancient pre-aqueous environment; (8) sugges-
tions for the design of verifying experiments (a cascade-flow
system).
The proposed model of hot organic stream is a geological
basis for an extremely fast start—“flash start”—of macro-
molecular evolution. Within our hypothesis, the problem of
“start temperature” (and the time required for the first stage
13
Journal of Molecular Evolution
of evolution) is solved easily, quickly, and topologically.
The period from volcanic eruption and prebiotic synthesis
of primeval organics in the hot (~ 300–400 °C) shock wave
zone—via condensation and formation of the stream—to the
emergence of macromolecular complexes and proto-cellular
structures in the cooled (~ 60–80 °C) liquid hydrated pond
took not million years but just several tens of minutes.
Acknowledgements  We are sincerely grateful to Vladimir Skoblikov
for valuable collaboration and to Alexey Agafonov who provided sub-
stantial assistance in preparing the English version of this text.
References
Adam ZR, Fahrenbach AC, Hongo Y, Cleaves HJ, Ruiqin Y, Yoda I,
Aono M (2017) Production and concentration of water-alternative
solvents on the prebiotic Earth. In 18th International Conference
on the Origin of Life 2017, p 4204
Adamala KP, Engelhart AE, Szostak JW (2016) Collaboration between
primitive cell membranes and soluble catalysts. Nat Commun
7:11041. https​://doi.org/10.1038/ncomm​s1104​1
Ahnert SE, Marsh JA, Hernández H, Robinson CV, Teichmann SA
(2015) Principles of assembly reveal a periodic table of protein
complexes. Science 350(6266):aaa2245. https​://doi.org/10.1126/
scien​ce.aaa22​45
Bada JL, Chalmers JH, Cleaves JH (2016) Is formamide a geo-
chemically plausible prebiotic solvent? Phys Chem Chem Phys
18:20085–20090
Bar-Nun A, Bar-Nun N, Bauer SH, Sagan C (1970) Shock synthe-
sis of amino acids in simulated primitive environments. Science
168(3930):470–473
Basiuk VA, Navarro-Gonzalez R (1996) Possible role of volcanic
ash–gas clouds in the Earth’s prebiotic chemistry. Orig Life Evol
Biosphere 26:173–194
Benner SA (2014) Paradoxes in the origin of life. Orig Life Evol Bio-
sph 44(4):339–343. https​://doi.org/10.1007/s1108​4-014-9379-0
Benner SA, Kim HJ, Carrigan MA (2012) Asphalt, water, and the
prebiotic synthesis of ribose, ribonucleosides, and RNA. Acc
Chem Res 45(12):2025–2034. https:​ //doi.org/10.1021/ar2003​ 32w
Bernal JD (1951) The physical basis of life. Routledge and Kegan Paul,
London
Brinkmann V, Reichard U, Goosmann C, Fauler B, Uhlemann Y, Weiss
DS, Weinrauch Y, Zychlinsky A (2004) Neutrophil extracellular
traps kill bacteria. Science 303(5663):1532–1535
Callahan MP, Smith KE, Cleaves HJ 2nd, Ruzicka J, Stern JC, Glavin
DP, House CH, Dworkin JP (2011) Carbonaceous meteorites
contain a wide range of extraterrestrial nucleobases. Proc Natl
Acad Sci USA 108(34):13995–13998. https​://doi.org/10.1073/
pnas.11064​93108​
Cavalier-Smith T (2001) Obcells as proto-organisms: membrane hered-
ity, lithophosphorylation, and the origins of the genetic code, the
first cells, and photosynthesis. J Mol Evol 53(4–5):555–595
Cleaves HJ 2nd, Michalkova Scott A, Hill FC, Leszczynski J, Sahai N,
Hazen R (2012) Mineral-organic interfacial processes: potential
roles in the origins of life. Chem Soc Rev 41(16):5502–5525. https​
://doi.org/10.1039/c2cs3​5112a​
Commeyras A, Collet H, Boiteau L, Taillades J, Vandenabeele-Tram-
bouze O, Cottet H, Biron JP, Plasson R, Mion L, Lagrille O, Mar-
tin H, Selsis F, Dobrijevic M (2002) Prebiotic synthesis of sequen-
tial peptides on the Hadean beach by a molecular engine working
with nitrogen oxides as energy sources. Polym Int 51(7):661–665.
https​://doi.org/10.1002/pi.1027
Journal of Molecular Evolution
Cronin JR, Pizzarello S (1997) Enantiomeric excesses in meteoritic
amino acids. Science 275:951–955
Damer B (2016) A field trip to the Archaean in search of Darwin’s
warm little pond. Life (Basel) 6(2):21 https​://doi.org/10.3390/
life6​02002​1
Damer B, Deamer D (2015) Coupled phases and combinatorial selec-
tion in fluctuating hydrothermal pools: a scenario to guide experi-
mental approaches to the origin of cellular life. Life 5(1):872–887.
https​://doi.org/10.3390/life5​01087​2
de Duve C (1991) Blueprint for a cell: the nature and origin of life.
Patterson, Burlington, p 275
Ebisuzaki T, Maruyama S (2017) Nuclear geyser model of the origin
of life: driving force to promote the synthesis of building blocks
of life. Geosci Front 8(2):275–298
Emons H-H, Naumann R, Jahn K, Flammersheim H-J (1986) Ther-
mal properties of acetamide in the temperature range from
298 K to 400 K. Thermochim Acta 104:127–137. https​://doi.
org/10.1016/0040-6031(86)85191​-7
Ferris JP, Hill AR Jr, Liu R, Orgel LE (1996) Synthesis of long prebi-
otic oligomers on mineral surfaces. Nature 381(6577):59–61
Ferus M, Pietrucci F, Saitta AM, Knížek A, Kubelík P, Ivanek O,
Shestivska V, Civiš S (2017) Formation of nucleobases in a
Miller-Urey reducing atmosphere. Proc Natl Acad Sci USA
114(17):4306–4311. https​://doi.org/10.1073/pnas.17000​10114​
Fox SW, Harada K (1961) Synthesis of uracil under conditions
of a thermal model of prebiological chemistry. Science
133(3468):1923
Fox SW, Harada K, Kendrick J (1959) Production of spher-
ules from synthetic proteinoid and hot water. Science 1
129(3357):1221–1223
Glasby GP (2006) Abiogenic origin of hydrocarbons: an historical
overview. Resour Geol 56(1):85–98
Haldane JBS (1929) The origin of life. Ration Annu 148:3–10
Hanic F, Morvová M, Morva I (2000) Thermochemical aspects of
the conversion of the gaseous system C ­ O2–N2–H2O into a solid
ixture of amino acids. J Therm Anal Calorim 60:1111. https:​ //doi.
org/10.1023/A:10101​52901​749
Harada K, Fox SW (1964) Thermal synthesis of natural amino-
acids from a postulated primitive terrestrial atmosphere. Nature
201:335–336
Hazen RM, Sverjensky DA (2010) Mineral surfaces, geochemical
complexities, and the origins of life. Cold Spring Harb Perspect
Biol 2(5):a002162. https​://doi.org/10.1101/cshpe​rspec​t.a0021​62
Higgs PG, Lehman N (2015) The RNA world: molecular cooperation
at the origins of life. Nat Rev Genet 16:7–17
Johnson AP, Cleaves HJ, Dworkin JP, Glavin DP, Lazcano A, Bada JL
(2008) The Miller volcanic spark discharge experiment. Science
322:404. https​://doi.org/10.1126/scien​ce.11615​27
Keefe AD, Miller SL (1996) Potentially prebiotic syntheses of con-
densed phosphates. Orig Life Evol Biosphere 26:15–25
Khare B, Sagan C (1971) Synthesis of cystine in simulated primitive
conditions. Nature 232:577–579. https​://doi.org/10.1038/23257​
7a0
Kuan Y-J, Charnley SB, Huang H-C, Tseng W-L, Kisiel Z (2003)
Interstellar glycine. Astrophys J 593:848–867. https ​ : //doi.
org/10.1086/37563​7
Lahav N, White D, Chang S (1978) Peptide formation in the prebiotic
era: thermal condensation of glycine in fluctuating clay environ-
ments. Science 201(4350):67–69
Lathe R (2003) Fast tidal cycling and the origin of life. Icarus
168:18–22
Lavrentiev GA, Strigunkova TF, Egorov IA (1984) Abiological syn-
thesis of amino acids, purines and pyrimidines under conditions
simulating the volcanic ash-gas cloud. Orig Life Evol Biosphere
14:205–212
Li CY, Tseng JY, Morita K, MacKenzie JD (1992) ORMOSILS as
matrices in inorganic-organic nanocomposites for various optical
applications. In Proceedings of SPIE—The International Society
for Optical Engineering 1758. Sol–Gel Optics II, pp 410–419.
https​://doi.org/10.1117/12.13203​3
Ligterink NFW, Coutens A, Kofman V, Muller HSP, Garrod RT, Cal-
cutt H, Wampfler SF, Jorgensen JK, Linnartz H, van Dishoeck
EF (2017) The ALMA-PILS survey: detection of CH3NCO
towards the low-mass protostar IRAS. Mon Not R Astron Soc
469(2):2219–2229. doi.https​://doi.org/10.1093/mnras​/stx89​0
Markhinin EK, Podkletnov NE (1977) The phenomenon of forma-
tion of prebiological compounds in volcanic processes. Orig Life
3:225–235
Matthews CN (2000) The HCN world: establishing protein-nucleic acid
life. Orig Life Evol Biosph 30:292–293
McManus JJ, Charbonneau P, Zaccarelli E, Neer Asherie N (2016) The
physics of protein self-assembly. Curr Opin Colloid Interface Sci
22:73–79. doi.https​://doi.org/10.1016/j.cocis​.2016.02.011
Miller SL (1953) A production of amino acids under possible primitive
earth conditions. Science 117:528–529
Monnard P-A, Apel CL, Kanavarioti A, Deamer DW (2002) Influence
of ionic inorganic solutes on self-assembly and polymerization
processes related to early forms of life: implications for a prebiotic
aqueous medium. Astrobiology 2:139–152
Mulkidjanian AY, Bychkov AY, Dibrova DV, Galperin MY, Koonin EV
(2012) Origin of first cells at terrestrial, anoxic geothermal fields.
Proc Natl Acad Sci USA 109:E821–E830
Norris V, Reusch RN, Igarashi K, Root-Bernstein R (2014) Molecular
complementarity between simple, universal molecules and ions
limited phenotype space in the precursors of cells. Biol Direct
9:28
Nutman AP, Bennett VC, Friend CR, Van Kranendonk MJ, Chivas AR
(2016) Rapid emergence of life shown by discovery of 3700-mil-
lion-year-old microbial structures. Nature 537:535–538
Okazaki M, Yoshida Y, Yamaguchi S, Kaneno M, Elliott JC (2001)
Affinity binding phenomena of DNA onto apatite crystals. Bio-
materials 22:2459–2464
Paecht-Horowitz M (1974) The possible role of clays in prebiotic pep-
tide synthesis. Orig Life 5(1):173–187
Parker ET, Cleaves HJ, Dworkin JP, Glavin DP, Callahan M, Aubrey
A, Lazcano A, Bada JL (2011) Primordial synthesis of amines
and amino acids in a 1958 Miller ­H2S-rich spark discharge experi-
ment. Proc Natl Acad Sci USA 108(14):5526–5531
Pascal R, Boiteau L, Forterre P, Gargaud M, Lazcano A, Lopez-Garcia
P, Moreira D, Maurel M-C, Pereto J, Prieur D, Reisse J (2006)
Prebiotic chemistry–biochemistry–emergence of life (4.4–2 Ga).
Earth Moon Planets 98:153–203
Patel BH, Percivalle C, Ritson DJ, Duffy CD, Sutherland JD (2015)
Common origins of RNA, protein and lipid precursors in a cya-
nosulfidic protometabolism. Nat Chem 7(4):301–307. https​://doi.
org/10.1038/nchem​.2202
Peretó J, López-García P, Moreira D (2004) Ancestral lipid bio-
synthesis and early membrane evolution. Trends Biochem Sci
29:469–477
Pizzarello S, Huang Y, Becker L, Poreda RJ, Neeman RA, Cooper
G, Williams M (2001) The organic content of the Tagish Lake
meteorite. Science 293:2236
Ponnamperuma C (1965) Peptide synthesis from amino acids in aque-
ous solution irradiated with ultraviolet. Science 147:1572–1574
Proskurowski G, Lilley MD, Seewald JS, Früh-Green GL, Olson EJ,
Lupton JE, Sylva SP, Kelley DS (2008) Abiogenic hydrocarbon
production at lost city hydrothermal field. Science 319:604–607
Rauchfuss H (2008) Chemical evolution and the origin of life. Springer-
Verlag, Berlin Heidelberg, p 339
Rode BM (1999) Peptides and the origin of life. Peptides 20:773–786
13

Rodriguez-Garcia M, Surman A, Cooper GJT, Suárez-Marina I, Hosni
Z, Lee MP, Cronin L (2015) Formation of oligopeptides in high
yield under simple programmable conditions. Nat Commun 2015
6:8385. https​://doi.org/10.1038/ncomm​s9385​
Ross DS, Deamer D (2016) Dry/wet cycling and the thermodynamics
and kinetics of prebiotic polymer synthesis. Life 6(3):28 https​://
doi.org/10.3390/life6​03002​8
Saladino R, Crestini C, Ciciriello F, Costanzo G, Di Mauro E (2006)
About a formamide-based origin of informational polymers: syn-
theses of nucleobases and favourable thermodynamic niches for
early polymers. Orig Life Evol Biosph. 36(5–6):523–531
Saladino R, Botta G, Pino S, Costanzo G, Di Mauro E (2012) Genet-
ics first or metabolism first? The formamide clue. Chem Soc Rev
41(16):5526–5565. https​://doi.org/10.1039/c2cs3​5066a​
Schopf JW, Packer BM (1987) Early Archean (3.3-billion to 3.5-bil-
lion-year-old) microfossils from Warrawoona Group, Australia.
Science 237:70–73
Schwartz AW, Joosten H, Voet AB (1982) Prebiotic adenine synthesis
via HCN oligomerization in ice. Biosystems 15(3):191–193
Schwartz AW, Voet AB, Van der Veen M (1984) Recent progress in the
prebiotic chemistry of HCN. Orig Life Evol Biosphere 14:91–98
Segré D, Ben-Eli D, Lancet D (2000) Compositional genomes: prebi-
otic information transfer in mutually catalytic noncovalent assem-
blies. Proc Natl Acad Sci USA 97(8):4112–4117
Shapiro R (1987) Origins: a skeptic’s guide to the creation of life on
earth. Bantam Books, New York p 110. ISBN: 0-671-45939-2
Sigurdsson H, Houghton B, Rymer H, Stix J, McNutt S (1999) Ency-
clopedia of Volcanoes. Academic Press, Cambridge p 1417 ISBN:
9780080547985
Skoblikow NE, Zimin АА (2015) A search for relict ribonucleotide and
amino acid sequences that played a key role in the development of
the ribosome and modern protein diversity. Math Biol Bioinform
10(1):116–130. https​://doi.org/10.17537​/2015.10.116
Skoblikow NE, Zimin АА (2016) Hypothesis of lithocoding: origin
of the genetic code as a “Double jigsaw puzzle” of nucleobase-
containing molecules and amino acids assembled by sequential
filling of apatite mineral cellules. J Mol Evol 82(4):163–172. https​
://doi.org/10.1007/s0023​9-016-9736-x
Smith JV, Arnold FP Jr, Parsons I, Lee MR (1999) Biochemical evo-
lution III: polymerization on organophilic silica-rich surfaces,
crystal-chemical modeling, formation of first cells, and geologi-
cal clues. Proc Natl Acad Sci 96(7):3479–3485
13
Journal of Molecular Evolution
Snyder LE, Buhl D, Zuckerman B, Palmer P (1969) Microwave detec-
tion of interstellar formaldehyde. Phys Rev Lett 61(2):77–115.
https​://doi.org/10.1103/PhysR​evLet​t.22.679
Spinler K, Tian A, Christian DA, Pantano DA, Baumgart T, Discher
DE (2013) Dynamic domains in polymersomes: mixtures of poly-
anionic and neutral diblocks respond more rapidly to changes in
calcium than to pH. Langmuir 29(24):7499–7508. https​://doi.
org/10.1021/la304​602e
Steinman G, Lemmon RM, Calvin M (1965) Dicyandiamide: possi-
ble role in peptide synthesis during chemical evolution. Science
147(3665):1574–1575
Stoks PG, Schwartz AW (1982) Basic nitrogen-heterocyclic com-
pounds in the Murchison meteorite. Geochim Cosmochim Acta
46:309–315
Sutherland JD (2016) The origin of life—out of the blue. Angew Chem
Int Ed Engl 55(1):104–121. https​://doi.org/10.1002/anie.20150​
6585
Trail D, Watson EB, Tailby ND (2011) The oxidation state of Hadean
magmas and implications for early Earth’s atmosphere. Nature
480(7375):79–82. https​://doi.org/10.1038/natur​e1065​5
Villar G, Wilber AW, Williamson AJ, Thiara P, Doye JP, Louis
AA, Jochum MN, Lewis AC, Levy ED (2009) Self-assembly
and evolution of homomeric protein complexes. Phys Rev Lett
102(11):118106
Wächtershäuser G (2006) From volcanic origins of chemoautotrophic
life to Bacteria, Archaea and Eukarya. Philos Trans R Soc Lond
B Biol Sci 361(1474):1787–1806
Wegner J, Ceylan S, Kirschning A (2011) Ten key issues in modern
flow chemistry. Chem Commun 28;47(16):4583–4592. https:​ //doi.
org/10.1039/c0cc0​5060a​
Wing MR, Bada JL (1991) Geochromatography on the parent body
of the carbonaceous chondrite Ivuna. Geochim Cosmochim Acta
55:2937–2942. https​://doi.org/10.1016/0016-7037(91)90458​-H
Yousefi S, Simon H-U (2016) NETosis—does it really represent
nature’s “Suicide Bomber”? Front Immunol 7:328. https​://doi.
org/10.3389/fimmu​.2016.00328​
Zimmerman SB, Trach SO (1988) Effects of macromolecular crowding
on the association of E. coli ribosomal particles. Nucleic Acids
Res 25(14A):6309–6326