The Transition from

Geochemistry to
Biogeochemistry
Nita Sahai1, 2, 3 Hussein Kaddour1 and Punam Dalai1

1811-5209/16/0012-0389$2.50DOI: 10.2113/gselements.12.6.389

P
aradigm-changing discoveries about stellar and planetary evolution, Hills, Western Australia (Bell et
the survival of organic molecules and microorganisms under extreme al. 2015). Stromatolite-like struc-
tures discovered very recently in
conditions, and geochemical environments on early Earth and other Isua have been dated to ~3.7 Ga
planets are sparking a synergistic dialogue between geoscientists, chemists, (Nutman et al. 2016), and bacte-
and biologists to understand how life originated. To achieve this goal, we rial microfossil-like structures
have been dated at ~3.43 Ga in the
must (i) explain the non enzymatic synthesis of biologically relevant organic Strelly Pool Sandstone Formation,
molecules under geologically plausible conditions; (ii) overcome the rigid concep- Western Australia (Brasier et al.
tual dichotomy of the RNA world versus the metabolism-first hypotheses; 2015). Isotopic evidence for metha-
notrophy and sulfate appear at the
and (iii) develop high-throughput analytical systems to sample the myriad
much younger ages of ~2.8Ga to
possible combinations of environmental conditions to find those that could ~2.7 Ga.
initiate life. This issue of Elements highlight the roles of minerals and geochem-
ical environments in the emergence of protocells, the cell-like entities that Defining Life
and the Protocell
might have preceded the Last Universal Common Ancestor.
The evidence to date suggests
Keywords : Mineral interfaces, RNA world, ironsulfur world, RNApeptide that even the most primitive life,
world, origin of life, protocells, metabolism at least as preserved in the rock
record, was remarkably complex
and similar to modern bacteria.
INTRODUCTION Yet, there must have been some precursor cell-like entities
The Earth formed ~4.56 Ga and was initially a hot planet. in the pathway from simple inorganic molecules containing
But oceans, and perhaps even continental crust, may have C, H, O, N, P, and S to bacterial cells. Discovering this
existed as early as ~4.34.4 Ga (Wilde et al. 2001). During transitional process is at the heart of the origin of life field.
this period, Earth was dominated by intense komatiitic In order to simulate this process experimentally, one needs
volcanism. The first gases released would have been highly to define the characteristics of a living cell. The search for
reducing and contained H 2 , CH4 (methane), and NH3 extraterrestrial life also hinges on defining what exactly
(ammonia). Once the Earths core had formed, CO2, N2, life is and what biosignatures one should be looking for.
and H 2O then became the major volcanic outgases that But defining life has proven to be surprisingly difficult.
subsequently formed the Earths atmosphere, with practi- Nevertheless, it is widely accepted that all forms of extant
cally no CH4 and NH3 (Kasting et al. 1993). Earths water life are characterized by three fundamental features (Fig.1).
inventory may have come from volcanic outgassing and/ First, all cells should possess a lipid bilayer membrane that
or been delivered by comets, meteorites, and microme- defines cell boundaries, allows mass- and energy-fluxes
teorites. Similarly, organic compounds would have been across the membrane, facilitates signaling between the
synthesized within the early atmosphere (endogenously) cell and its environment, and serves many other essential
and delivered from space (exogenously). The ~3.8 Ga green- functions. Second, a universal DNARNA-based apparatus
stones in Isua (Greenland) indicate that permanent oceans acts to transmit genetic information from one generation to
existed by that time. Primitive oceans are estimated to the next. This apparatus also has the potential to mutate,
have been about twice as salty as modern oceans and were thereby allowing evolution by natural selection. Third, all
slightly acidic (pH ~56.5) during the Hadean. The date for cells need to possess metabolism, which may be described
the emergence of life is still highly debated. The scarcity as cycles of enzyme-catalyzed electron-transfer reaction
of rocks from the Hadean Eon and Eoarchean Era, plus networks to synthesize (anabolize) and to break-down
problems associated with post depositional alteration, make (catabolize) complex molecules (Fig. 2). These processes
it difficult to pin down a precise date. A very early date provide the necessary molecules and energy by which the
of ~4.1 Ga for the origin of life is based on light carbon cell can sustain itself and reproduce. Related to these three
isotope signatures from carbon inclusions in zircons of Jack characteristic features of life are the corresponding molec-
ular building blocks of life, namely, membrane-building
phospholipids, DNA/RNA and proteins, and a variety of
1 Department of Polymer Science critical small molecules such as the adenosine phosphates.
2 Department of Geology Although it is difficult to define life, it is widely assumed
3 Integrated Bioscience Program that self-replicating, cell-like entities called protocells
170 University Avenue, University of Akron possessed all the main characteristics of cells and preceded
Akron, OH 44325-3909 the Last Universal Common Ancestor (aka LUCA the
E-mail: [email protected]

E lements , V ol . 12, pp. 389394 389 D ecember 2016

organism from which all living organisms today descend). reactions forward in aqueous solutions while preventing
Today, most prokaryotes live in biofilm communities the degradation of the organics formed by hydrolysis in
attached to mineral surfaces, so it is reasonable to assume these aqueous environments. Even when polymerization
that the mineralwater interface would have provided a has been achieved, selecting functional molecules from
nursery for protocells and that minerals played a role in the huge combinatorial space of polymers to form self-
the synthesis and self-assembly of the earliest protocells. sustaining and reproducing entities is daunting and is yet
Specific minerals can even be shown to play the role of to be fully experimentally addressed.
certain enzymes (Fig. 1).
Geological Processes
and Geochemical Environments
The difficulty of synthesizing monomers from simple
starting compounds and subsequently polymerizing them
to achieve some type of functionality increases tremen-
dously when attempting to achieve these processes under
plausible early Earth geochemical environments and
geological processes. For example, some chemical syntheses
require very high concentrations of starting compounds
and may involve several steps, such as separation and purifi-
cation. What were the corresponding analogous geological
processes? Evaporation, sublimation, rehydration, and
others, have all been proposed. But then these processes
would need to have occurred in just the right sequence and
needed just the right environmental conditions that were
used in the experiments (temperature, pressure, pH, etc.).
Thus, it is important to consider synthetic scenarios that
would be geologically plausible to capture at least a slightly
more realistic situation for the origin of life.
Estimating conditions that existed on early Earth relies on
Schematic showing the minimal characteristics of all
Figure 1 the rock record from the Hadean and early Archean. But
known extant cells. A semipermeable membrane (blue
circle) for mass transport into and out of the cell; an enzyme- this is sparse, not least because plate tectonics recycles the
catalyzed self-replication reaction (inside left) and an enzyme- crust efficiently. Nonetheless, despite much debate among
catalyzed transmembrane redox reaction network (metabolism; far geoscientists about the ranges of early Earths atmospheric
right). E1E3 are enzymes. Methanogenesis (CH4 production; lower
right) is shown as an example of an early metabolism; minerals play
composition, there are certain generally accepted condi-
the role of some pre-enzymatic catalysts in protocells. The protocell tions. The high partial pressure of CO2 gas on Hadean
is shown living a sessile life attached to a mineral surface, similar to Earth would result in an acidic pH (~56) for surface
many modern biofilm communities. waters. Alkaline solutions (pH ~10) would be formed in
regions where peridotitic mantle was being serpentinized.
Estimates for inorganic ion concentrations in such scenarios
Prebiotic Chemistry may be obtained based on thermodynamic calculations
DNA/RNA and proteins are polymers of nucleotide of atmospherewaterrock interactions (Schoonen and
monomers and of amino acids. The production of these Smirnoff 2016 this issue).
genetic molecules involves enzymatically catalyzed In addition to organic molecules being synthesized on
polymerization of nucleotide monomers. However, the Earth, organics may also have been delivered from space by
synthesis of the enzymes (catalytic proteins) and of all meteorites and cosmic dust particles, where the synthesis
proteins requires DNA/RNA. The production of membrane- would have occurred under very different environmental
forming phospholipids is also enzymatically catalyzed. conditions from those on early Earth. Extreme cold
Thus, the origin of life is a prime example of a chicken- temperatures, vacuum-like pressures, and high UV radia-
and-egg problem, because enzymes are needed to produce tion conditions would have been present in space. And,
DNA/RNA, yet DNA/RNA are needed to produce proteins, organic molecule synthesis may also be possible under
including enzymes. Thus, before life originated, what conditions on other planets and their satellites, such as
molecules and minerals could have served as prebiotic Enceladus and Titan (two moons of Saturn).
catalysts for the polymerization of nucleotides and amino
acids into DNA/RNA and proteins, respectively? RNA World versus Metabolism-first Theories
It is not only the polymerization of nucleotides and There are several origin of life hypotheses currently being
amino acids that is problematic. Even the preceding step researched, and it is worth briefly reviewing them.
involving the synthesis of monomers from much simpler Some researchers in the origin of life field believe that
starting compoundssuch as N2 , CO2 , H 2O, HCN, SO2 the synthesis of DNA is too complex to have occurred
and H2 S, which would have been present in the Hadean without the input of enzymes. The molecule RNA is an
and early Archean atmospherespresents an equally diffi- information-carrier, and, thus, the discovery that some
cult challenge. The difficulties arise from multiple causes. RNAs can act as enzymes led to a hypothesis that early
First, carbon is generally in the reduced form in organic life was RNA-based (Gilbert 1986). This is the well-known
compounds, whereas it was the oxidized form of carbon RNA world hypothesis (Box 1).
in CO2 that was most likely the stable form of carbon on
early Earth. Achieving sufficient reactant concentrations Others have argued that even the synthesis of RNA is
of reduced carbon to yield products in viable quantities difficult and that prebiotic catalytic molecules must have
under plausible geological conditions and without enzymes evolved first to create reaction networks for the synthesis
is difficult. Many synthesis reactions, as well as the subse- of the molecular building blocks. This is called the metab-
quent polymerization reactions, involve condensation olism-first theory. The role of iron sulfide minerals and
reactions. Another major concern is how to drive such thioacids in the emergence of the earliest metabolic cycles

E lements 390 D ecember 2016

 This complex process of going from inorganic molecules
Box 1 TEN KEY ARGUMENTS FOR THE RNA WORLD
HYPOTHESIS.
to protocells will be presented in stages. The reactions of
inorganic molecules to form simple organic compounds
1. RNA can carry genetic information (e.g. RNA viruses) (such as amino acids, nucleotides, sugars, single chain
2. RNA is a single-stranded, flexible molecule that can adopt fatty acids, and small molecules used in metabolism) is
tertiary structures covered in Dalai et al. (2016 this issue); Maurel and Leclerc
3. RNA is less stable than DNA (therefore, through the (2016 this issue) and Belmonte and Mansy (2016 this issue)
evolution rationale, DNA should have come later) consider the next step, which involves the formation of
4. Thymine, a nucleobase of DNA, is a methylated uracil, polymers and complexes of nucleotides and peptides; and
a nucleobase of RNA (methylation is often considered a Kee and Monnard (2016 this issue) provide a perspective
reaction for preserving biomolecules) on the importance of encapsulation by a lipid membrane to
5. An RNA primer is essential for DNADNA replication form a protocell. Third, the need for new ways of thinking
6. Natural reverse transcriptase is an enzyme that copies RNA
about the origin of life problem, possibly by considering
into DNA that genetic and metabolic molecules evolved cooperatively
and synergistically.
7. RNA is deeply implicated in peptide bond synthesis
(e.g. mRNA, tRNA, rRNA) In general, addressing these three broad themes is essen-
8. RNA is deeply implicated in gene regulation (e.g. tial to bridging the considerable gap that currently exists
self-splicing RNA, riboswitches, siRNA) in origin of life studies between biochemists/organic
9. A repertoire of biochemical functions can be achieved by chemists on the one hand and geochemists/mineralogists
RNA (e.g. aminoacylation, RNA cleavage, RNA ligation). on theother.
10. Ribozymes have been discovered to be widespread in all
domains of life. GEOCHEMICAL EVOLUTION OF AQUEOUS
SOLUTIONS ON EARLY EARTH
Life has been found in almost every environmental niche
before RNA is called the ironsulfur world hypothesis on Earth. Therefore, is it possible that life could have
(Wchtershuser 1990). Another model proposes that the flourished under early Earth environmental conditions as
acetyl coenzyme A (acetyl-CoA) pathway linked to a chemi- well. What were the potential aqueous solution composi-
osmotic membrane potential provided the earliest metabo- tions and temperatures on early Earth? The weathering of
lisms (Sousa et al. 2013; Russell et al. 2014; Lane 2015). different rock types under Hadean/Archaean atmospheric
The RNA world versus metabolism-first debate has been compositions and the variety of ocean vent chemistries
raging for the past seven decades (Lazcano 2008). However, would have controlled the types of aqueous solution
recent advances suggest that neither hypothesis is exclu- chemistries and the suite of secondary minerals that formed
sively correct. Both RNA and other catalytic molecules may in the geological settings of the time. Particular solution
have evolved contemporaneously and, potentially, even chemistries and species of minerals present would have
cooperatively (Kaddour and Sahai 2014). provided different environmental niches for the origin
and sustainability of life. Similar conceptual approaches
In this issue, three main themes are highlighted. First, the can be envisioned for environments on Mars and other
critical importance of using geochemically relevant environ- rocky planets. When discussing the origin of life in terres-
mental conditions plausible on early Earth for designing trial environments, most studies focus on subaerial and
experiments that model the emergence and early evolution subaqueous environments; but subsurface environments
of life (Schoonen and Smirnov 2016 this issue). Second, the and the interface between the two is often not consid-
potential role that minerals, dissolved inorganic ions, and ered. For example, the interface between the open and
ion-clusters (acting as catalysts or as reactants) play in the closed carbonate systems, provided by the hydrologic water
prebiotic synthesis of the molecular building blocks of life.

A B

1 2

ADP

3 4
ATP
5

Copyright2004PearsonEducation,Inc.,publishingasBenjaminCummings

(B) Five main molecular building blocks of life. (1) cytidine

(A) Metabolism comprises both anabolism (making monophosphate; (2) guanosine monophosphate; (3) amino acid
Figure 2
molecules) and catabolism (breaking up molecules. with side chain -R; (4) palmitic acid, a single chain fatty acid
ADP (adenosine diphosphate); ATP (adenosine triphosphate). Used (single chain amphiphiles have been proposed to be precursors
with permission of Pearson E ducation, I nc. from Tortora et al . (2016) to phospholipids which form the membranes of modern cells);
Microbiology: An Introduction, 12th Edition, p 110, Fig. 5.1. (5)palmitoyl-oleoylphosphatidylcholine, a phospholipid.

E lements 391 D ecember 2016

table, is such an environment across which a chemical METAL SULFIDES AND METALLOPEPTIDES
gradient can be maintained. Schoonen and Smirnov (2016 IN PROTOMETABOLISM
this issue) address these themes using equilibrium thermo-
Given the very large number of prebiotic organic molecules,
dynamics speciation calculations to determine aqueous
as well as the complexes they potentially made with metals
solution compositions and secondary mineral assemblages
and other organics that might have existed on early Earth,
under a range of environmental conditions and rock types
it is theoretically possible that a huge number of reaction
on early Earth.
networks could have formed. However, Morowitz and
coworkers (e.g. Smith and Morowitz 2010) have recognized
PREBIOTIC SOURCES OF SIMPLE that modern metabolisms utilize a very small number
ORGANICMOLECULES (~300) of metabolites compared to the vast number of
Organic compounds had to be present before life began. molecules possibly formed from random chemical combi-
Simple compounds such as N2, CO2, HCN, SO2, and H2 S nations. Morowitz and coworkers have argued that this
must have been polymerized into larger compounds with sparse metabolism reflects selection based on chemical
complex structures and functionality, eventually leading to kinetics. In this scenario, specific reactions are selected by
their self-assembly into a protocell. What were the sources small-molecule organocatalysts. These are distinct from
of the starting organic compounds that ultimately yielded transition metalorganic complex catalysts (discussed
protocells, and how could they have accumulated on early below). Some small-molecule organocatalysts are even
Earth? The total inventory of organics would have included capable of enantioselectivity [choosing between L and
both exogenous sources (cosmic dust, comets, meteorites) D molecular forms]. The reductive citric acid cycle was
and endogenous sources. On Earth, organics would have proposed as a core metabolism that could produce all
been formed in the atmosphere, in solution, and at the the building blocks of life. A different perspective was
mineralwater interface in subaerial, subaqueous, and offered by Virgo and Ikegami (2013) based on the results
subsurface environments. of computer algorithms of abstract model reactions. These
authors showed that intersecting, branching, autocata-
A fascinating feature of life is its homochiral nature, and
lytic reaction networks form easily without the need for
homochirality [handedness of molecules: laevorotatory,
an initial catalytic molecule to be present. Virgo and
or L, for left-handed symmetry; dextrorotatory, or D, for
Ikegami (2013) argued that the earliest metabolisms were
right-handed symmetry] has often been assumed to be a
maximal and that the reductive citric acid cycle, or
biosignature. However, amino acids from carbonaceous
other minimal metabolic systems, were derived by later
chondrite meteorites also show an enrichment of L- over
evolution. Whereas many hypothetical schemes modeling
D-isomers, even for those amino-acids not utilized by
metabolic reactions exist in the literature, experiments that
biology. These results suggest that chiral selection may have
simulate metabolic reactions or that couple more than one
occurred before life originated and may not be a biosig-
reaction into a cycle is a major challenge.
nature. So, by what processes could homochirality have
arisen? Dalai et al. (2016 this issue) provide an overview In modern metabolic pathways, the active sites of many
of the natural prebiotic sources of organics, the results enzymes contain organometallic complexes, in particular,
of experiments that attempt to simulate exogenous and ironsulfur clusters. The metalsulfur clusters of enzymes
endogenous organic synthesis, and the potential mecha- are structurally similar to greigite and other sulfide
nisms for chiral selection. minerals. This similarity in structure has led to sugges-
tions that metabolic pathways developed in the presence
RNA, PEPTIDES, AND MINERALS of sulfide minerals. The ironsulfur world hypothesis and
the acetyl-CoA chemiosmotic potential model propose that
As mentioned above, DNA is considered to be too complex
metabolic networks developed before RNA. Belmonte and
to have been synthesized abiotically, while RNA has
Mansy (2016 this issue) broaden this concept to explore
proven to be a versatile alternative biomolecule that,
other metals and peptides in a scenario where various simple
since its structural elucidation, has kept on surprising
catalytic metallopeptide complexes may have predated
us. Indeed, RNA has characteristics similar to DNA as
more complex enzymes. By analyzing modern bacteria,
a genetic molecule. Furthermore, many vital cellular
these authors identified that specific peptide sequences
functions, previously thought to be exclusive to proteins,
that contain aspartic acid (aspartate) are important for
have been found to be achieved by specific types of RNA.
binding Mg2+, Mn 2+, Zn 2+, and Ni 2+, whereas sequences
For example, ribozymes are small RNA motifs that have
that contain cysteine (an amino acid that has a SH side
catalytic activity; riboswitches are regulatory segments of
chain) are important for binding Fe2+. The identification
messenger RNA (mRNA). These discoveries, together with
of such peptide sequences could provide a guiding light for
several additional arguments, support the current idea that
designing experiments to simulate ancient metabolisms.
life may have originated by self-replicating RNA molecules,
which preceded the DNA/RNA/protein world (Box 1).
TOWARD A PROTOCELL: ASSEMBLING
Could minerals have shaped the ancient RNA world? Clays THECOMPONENTS OF LIFE
can catalyze the polymerization of nucleotides and amino
A membrane boundary composed of amphiphilic
acids to form RNA oligomers and peptides, respectively.
compounds [ones that possess both hydrophilic and
Beyond the RNA world hypothesis, metal sulfides may have
lipophilic properties] and that is assembled into a vesicle
played roles such as catalyzing peptide synthesis. Peptide
compartment is one of the key elements of life (Figs . 1
RNA complexes may have been endowed with special
and 2). The membrane defines the cell as a distinct entity,
functions, ones that either RNA alone or peptide alone
separate from the environment, and plays a critical role
could not have achieved. Maurel and Leclerc (2016 this
in the production and maintenance of the chemiosmotic
issue) address the potential role of minerals in the synthesis
potential (charge and pH gradients) required to drive
and self-assembly of RNA and RNApeptides. These authors
cellular reactions. Modern cell membranes consist primarily
also explore the fascinating idea that viroidsshort
of phospholipid molecules, but their synthesis is enzymati-
segments of RNA found in nature as plant parasitesare
cally catalyzed. So, what was the chemical composition of
a sort of molecular fossil from a former RNA world.
the protocell boundary? The walls of microscopic pores
between mineral grains in rocks or channels in zeolites

E lements 392 D ecember 2016

have been proposed by some workers to act as the earliest nucleotides can be spontaneously generated in prebioti-
membranes but these ideas havent been thoroughly cally relevant conditions. Moreover, the yields of these RNA
tested experimentally. On the other hand, single-chain oligomers are rather low, barely enough to be character-
amphiphilic molecules have been identified in meteorites ized by the most sensitive techniques. Recent efforts have
and synthesized nonenzymatically, so lipid membranes showed that nonenzymatic RNA polymerization can be
may have self-assembled in the earliest protocells. What are alternatively achieved by using nonactivated monomers
the physicochemical conditions for the stability of either (poner et al. 2016).
the pore-wall membranes or amphiphile membranes? The
Taken together, these findings have led to the idea that
term stability here refers to membrane formation and its
synergism between different catalysts might come into
ability to sustain integrity over some relevant period of
play to enhance the nonenzymatic RNA polymerization of
time (i.e. membranes needed the right balance of leakiness
nonactivated nucleotides (Fig. 4) (Kaddour and Sahai 2014).
versus impermeability to allow molecules and electrons
to pass across the membrane to generate electrochemical
gradients long enough for the relevant metabolic reactions).
How would the organics encapsulated within either of these earlyEarthatmosphere CO2,H2O,N2,SO2,H2,H2S
types of membranes have evolved into a complex network
to give birth to a sustainable protocell? Could minerals
have played a role in all these processes? Kee and Monnard abioticchemistry hydrogencyanide(HCN),formamide(HCONH2),
formaldehyde(H2CO)
(2016 this issue) address these important questions and
discuss the critical need of a protocell boundary to form
self-sustaining, replicating, cell-like entities. nucleotides,aminoacids,singlechain
prebioticorganicchemistry amphiphiles
SYNERGISM AND MUTUALISM
IN THE EMERGENCE OF LIFE oligomerization shortRNA lipidvesicles small
oligomers assembly peptides
Significant advances have been made over the past decade
in our understanding of the simple organic molecule
mineral interactions that yield more complex organic protocellsencapsulatingsmallRNAoligomers
compartmentalization andpeptides
molecules (Cleaves et al. 2012). We presently also benefit
from a much-improved knowledge of early Earth environ-
ments (Sleep et al. 2011). In addition, experiments have polymerization& invesiculohairpinRNAoligomersandsmall
shown that specific minerals can play some key roles as naturalselection catalyticpeptides
prebiotic enzymes. For example, montmorillonite can
catalyze the formation of RNA polymers (Ferris 2005) and RNApeptideworld aptamerligandcomplexes;functionalRNAs
of peptides (Rode 1999); sphalerite (ZnS) can photocatalyze &naturalselection andcatalyticpeptides
parts of the reverse citric acid cycle (Zhang and Martin
2006). Minerals can also enhance the initial assembly
rate of amphiphiles into vesicles, ultimately leading to life cells
the formation of a protocell membrane (Hanczyc et al.
2003). The latter finding was recently confirmed in our
Hypothetical stages in the emergence of an RNA
laboratory and we further showed that the rate-enhance- Figure 4
peptide world on early Earth. The exact sequence of
ment is dependent on the surface charge of the mineral. events, especially at the intermediate stages involving compartmen-
Additionally, we found that vesicles were not disrupted talization, polymerization, and natural selection, is unknowable and
by high particle loadings and they can even adsorb intact can only be conjectured.
on a mineral surface (Fig.3; Sahai et al. 2017). Together,
these results suggest that minerals should be given more
attention in the context of the emergence of life. MULTICOMPONENT SYSTEMS
ANDPREDICTIVE RELATIONSHIPS
That being said, a careful analysis of the literature raises
It is obvious that nature cannot be minimized to a single-
interesting questions. For instance, in the pioneering
component system in a clean test tube. The results of exper-
work of Prof. James P. Ferris (Rensselaer Polytechnic, New
iments aimed at understanding the prebiotic synthesis
York, USA) and colleagues, only chemically pre-activated
and self-assembly of organics would be significantly more
monomers were used to react and polymerize into RNA
relevant in a multicomponent system. Thus, in an ideal
oligomers; even though it is unlikely that such activated
experiment, the molecular building blocks of life should
be present along with the minerals and dissolved inorganic
ions known to exist in specific geological environments on
early Earth. Recent attempts towards a one-pot reaction
approach have been successful in the synthesis of lipid
monomers, amino acids, and nucleotides (Patel et al. 2015).
It would also be a remarkable achievement to expand this
approach to the emergence of a sustainable protocell. In
this regard, researchers have been synthesizing chemical
systems where nonenzymatic RNA polymerization occurs
in model protocells (Szostak 2012). With these significant
advances, evaluating the potential complicating effects of
inorganic ions, pH, and temperature in a multicomponent
system should now be considered as next steps towards
integrating chemistry and biology with geology.
Cryo-transmission electron microscope images, taken
Figure 3
in media of pH 7.8, of model protocells in contact Exploring a wider range of environmental conditions
with mineral surfaces. (left) Decanoic acid vesicles and montmoril- are hampered by difficulties in experimental design and
lonite. ( right) Decanoic acid vesicles and anatase.

E lements 393 D ecember 2016

analytical sensitivity. For example, it can be difficult to of environmental conditions on early Earth are preserved
analyze reactants and products within model protocell in the isotope and element signatures of rare Hadean-
membranes (amphiphile vesicles). This is especially the case and Eoarchean-age minerals and rocks, but the molecular
in experiments involving mineral suspensions, which tend pathways from simple inorganic compounds to cells cannot
to aggregate and settle, thereby minimizing interactions be retraced with complete fidelity. Nevertheless, chemical
with the other components. Furthermore, most reactions pathways that rigorously satisfy scientific rationale can
are done in batch systems, and geological processes such be reasonably inferred based on the results of models
as fluid flow and wave action are hardly ever simulated and experiments that are informed by our knowledge
in the experimental design. High-throughput analytical of the biochemistry of modern life and of early Earths
methods are sorely needed to test the huge combinato- environmental conditions. We hope that the present
rial search space that must be explored in order to more issue of Elements illuminates the state-of-the-art in the
faithfully simulate geological conditions. Careful exami- field, indicates challenging areas for future inquiry, and
nation of a wide range of conditions will ultimately allow inspires scientists to adopt interdisciplinary approaches
the development of predictive relationships. For example, towards uncovering one of the most profound questions
the initial rate of vesicle self-assembly at mineral surfaces in philosophy and science.
has been found to be dependent on the isoelectric point
(surface-charge) of the mineral and on the degree of aggre- ACKNOWLEDGMENTS
gation of mineral nanoparticles (Sahai et al. 2017). Such The authors are grateful to Dr. Min Gao, Liquid Crystal
relationships may allow us to predict the plausibility of Institute, Kent State University for the cryo-TEM images
protocell membrane self-assembly both terrestrially and and to Dr. Weilong Zhao for coloring the banner image.
extraterrestrially. N. S. and H. K. would like to thank the authors of the
invited articles in this issue as well as the reviewers of the
CLOSING REMARKS manuscripts for their invaluable contributions to this issue.
The ultimate challenge in the origin of life field is to Patricia Dove and Jodi Rosso are thanked for their edito-
understand how complex, functional organic molecules rial insights. Nita Sahai gratefully acknowledges financial
were produced from simple inorganic molecules and how support from the following grants: NSF EAR Geobiology
such molecules self-assembled into self-sustaining, self- and Low-Temperature Geochemistry #1251479; the Simons
replicating cell-like entities under plausible environmental Collaboration on the Origins of Life (SCoL) award #290359
conditions on early Earth. This means understanding the from the Simons Foundation, NY; and startup funds from
transition from geochemistry to biogeochemistry. Traces the University of Akron.

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