Abstract
Earth's 4.5-billion-year history has witnessed a complex sequence of high-probability chemical and physical processes, as well as ‘frozen accidents’. Most models of life's origins similarly invoke a sequence of chemical reactions and molecular self-assemblies in which both necessity and chance play important roles. Recent research adds two important insights into this discussion. First, in the context of chemical reactions, chance versus necessity is an inherently false dichotomy—a range of probabilities exists for many natural events. Second, given the combinatorial richness of early Earth's chemical and physical environments, events in molecular evolution that are unlikely at limited laboratory scales of space and time may, nevertheless, be inevitable on an Earth-like planet at time scales of a billion years.
This article is part of the themed issue ‘Reconceptualizing the origins of life’.
Keywords: origins of life, stochasticity, mineralogy, terrestrial planets, false dichotomies
The universe is not pregnant with life nor the biosphere with man…Man at last knows that he is alone in the unfeeling immensity of the universe, out of which he emerged only by chance.
(Jacques Monod, Chance and Necessity, 1970)
The origin of life and evolution were necessary because of conditions on Earth and the existing properties of the elements.
(Ernest Schoffeniels, Anti-Chance, 1976)
1. Introduction
Chance or necessity? Are profound cosmic transitions reducible to this stark choice, or is such a polarized dichotomy false? In a Universe rich in emergent, evolving systems—stars and planets, elements and isotopes, life and the conscious brain, society and culture—we ask which phenomena are inevitable as opposed to those that are frozen accidents? Events in the ‘messy’ natural world arise from lawful physical and chemical processes, but the physico-chemical conditions required for some phenomena to occur may be highly improbable. In no domain of inquiry is this situation more relevant, yet more challenging, than life's ancient origins. Is the transition from geochemistry to biochemistry an intrinsic characteristic of virtually all ‘Earth-like’ planets, or does life's emergence require a combination of physical and chemical conditions that occurs only infrequently in the cosmos?
Scientists and philosophers have taken stands on both sides of this debate. Jacques Monod [1] famously viewed life's origins in general, and our existence in particular, as a matter of chance, unlikely to be replicated elsewhere in the Universe—a position echoed in more recent analyses [2]. Others countered with the view that life is a cosmic imperative—an inevitable consequence of the chemical and physical environments of warm, wet terrestrial planets [3,4].
Two quantitative concepts, both inspired by consideration of the origins of life from a physical sciences perspective, may help to inform this discussion. The first concept relates to probabilities of chemical reactions on Earth. Life's origin was a sequence of steps—chemical reactions and molecular self-assembly—each of which added structure and complexity to Earth's near-surface environment. These steps culminated in a self-replicating, self-sustaining, carbon-based molecular system subject to mutation, selection and, consequently, rapid evolution [5–9]. It is not yet possible to estimate probabilities of most organic chemical reactions on the prebiotic Earth, much less to define the sequence of chemical reactions and self-assemblies that led to the first living cell. However, we gain key insights from mineralogy because each of the more than 5000 approved mineral species (each defined by its unique combinations of crystal structure and chemical composition) represents a chemical reaction. The frequencies of occurrence of these diverse mineral species thus point to the probabilities that the requisite physical and chemical conditions for their formative chemical reactions obtain. Some physico-chemical conditions necessary for mineral-forming reactions to occur are more probable than others; hence, a stark division of such natural processes into chance versus necessity is an inherently false dichotomy.
The second, semi-quantitative, insight relates to the character of Earth-like planets, which promote chemical reactions in varied near-surface environments. Here, we estimate the numbers of plausible surface-mediated chemical reactions that might occur at the spatial and temporal scales of planets, thus demonstrating that reactions that are improbable to observe at restricted scales of laboratory experiments may, nevertheless, be inevitable in the grand combinatorial context of terrestrial worlds. We conclude, again, that framing life's origins in the polarizing context of ‘chance versus necessity’ creates a false dichotomy.
2. Probabilities of mineral-forming reactions
Minerals and life coevolved, with most mineral species mediated by life [10]. Thus we postulate that mineral-forming and life-forming chemical reactions follow similar patterns. This parallel extends to many aspects of mineralogy and biogenesis. For example, new minerals and life's molecular structures, alike, require concentration mechanisms, including gradients, fluxes, cycles and interfaces, to promote selection and assembly of the necessary elemental and molecular building blocks [11].
In 2015, we discovered that the diversity and global distribution of mineral species follow statistical patterns analogous to the arrangement and frequency of words in a book [12–15]. Whereas a few words such as ‘a’, ‘and’ and ‘the’ are common in any book, the majority of different words are used rarely, many only once or twice. On Earth, the resulting ‘large number of rare events’ (LNRE) distribution of minerals facilitates calculation of probabilities for each species—i.e. the probabilities for more than 5000 chemical reactions. We find that some reactions are all but inevitable, others highly unlikely—extremes that might be characterized as necessity versus chance. However, many mineral species occur sparsely, their formation being dependent upon the occurrence of ancillary reactions and seldom-encountered physico-chemical conditions, and hence they possess intermediate probabilities. We conclude that ‘chance versus necessity’ in the context of prebiotic chemical reactions is an inherently false dichotomy.
In an effort to deduce the nature of probability distributions for chemical reactions on Earth, we focus on Earth's well-documented mineral-forming chemical reactions. Earth's more than 5000 mineral species (as approved by the International Mineralogical Association: http://rruff.info/ima/) conform to a LNRE frequency distribution [12–15] (figure 1). A few minerals are abundant, with fewer than 100 common minerals accounting for more than 99% of Earth's crustal volume, and a handful of feldspar mineral species comprising approximately 60 vol% [16,17]. However, most mineral species are extremely rare, identified from five or fewer localities worldwide. These seldom-seen mineral species are rare for a variety of reasons [18], but most of them arise only in a restricted environment with an improbable combination of physical and geochemical conditions—environments that may occur on only a small fraction of all terrestrial planets. Because this observed distribution of mineral species on Earth is analogous to that of words in a book, modification of lexical statistics facilitates application of LNRE models to characterize the diversity and distribution of Earth's minerals [19,20].
Figure 1.

Observed (black, left bars) and modelled (red, right bars) frequency distribution for rare minerals on Earth (GIGP = generalized inverse Gauss–Poisson). Most of Earth's more than 5000 mineral species are rare, occurring at five or fewer localities [12,14]. They conform to an LNRE frequency distribution, which mimics the distribution of words in a book. (Online version in colour.)
The LNRE model facilitates calculation of accumulation curves as employed in biology as a means to predict what minerals exist on Earth but have yet to be discovered and described. We predict the existence of more than 6400 minerals on Earth, suggesting that more than 1000 species await discovery (figure 2). Note that this total represents a relatively small fraction of the estimated more than 15 000 plausible minerals that probably occur on one or more terrestrial planets throughout the cosmos [12]. We conclude that many thousands of potential mineral species are not found on Earth but occur on terrestrial planets elsewhere in the Universe.
Figure 2.

The accumulation curve for Earth's minerals, calculated from LNRE systematics [14,15], reveals that more than 6400 mineral species may occur on Earth, more than 1000 of which have yet to be discovered and described. (Online version in colour.)
LNRE systematics also facilitate the estimation of the ranked probabilities of all 6437 known and predicted mineral species on Earth (figure 3), as described by Hystad et al. [14,15]. We find that more than 2000 species are extremely likely, with probabilities close to 100% on any planet with a physical environment and bulk chemical composition similar to Earth's—hence, these species are inevitable aspects of Earth's mineralogy. On the other hand, several hundred of Earth's mineral species are relatively unlikely, with probabilities of occurring on fewer than 10% of planets with physical and chemical properties similar to Earth's, and thus might be viewed as ‘frozen accidents.’ Most minerals, however, have intermediate probabilities; we predict that they occur on between 10% and 90% of terrestrial planets with chemical and physical properties similar to Earth's, and thus are the products of neither necessity nor chance.
Figure 3.

The ranked probabilities of 6437 observed and predicted mineral species that exist on Earth (from a population of more than 15 000 likely mineral species distributed on all Earth-like planets in the cosmos) reveal that some minerals are inevitable on an Earth-like planet, others highly unlikely, but many display intermediate probabilities [15]. (Online version in colour.)
It is not yet established whether the probabilities of organic chemical reactions follow a relationship similar to that of figure 3. However, it is certain that such prebiotic reactions will display a range of probabilities, with numerous reactions occurring concurrently on Earth and some reactions more likely than others [21]. Thus, for example, the amino acids glycine and alanine form under a wide range of prebiotic conditions when C, H, O and N are present, whereas several essential amino acids have not yet been synthesized under plausible prebiotic conditions or observed in carbonaceous meteorites [22–31]. We conclude that the sequence of chemical reactions that led from geochemistry to biochemistry cannot be reduced to a binary choice between chance and necessity.
3. Combinatorial richness of Earth's chemical reactions
Probabilities of chemical reactions must be considered in the context of terrestrial planets and moons. We suggest that terrestrial planets, owing to their vast spatial and temporal scales, as well as their stunning diversity of near-surface physical and chemical environments, have the potential to sample immense ranges of chemical reaction ‘space’. Here, we conceive of the origins of life as a sequence of surface-mediated chemical reactions (with a bias towards chemical reactions promoted by diverse mineral surfaces), and we ask how many such reactions might have occurred on prebiotic Earth. Earth-like planets possess fine-grained clays, volcanic ash deposits, weathering zones, and other exposed minerals with total surface areas that greatly exceed that of the planetary surface—a vast mineral surface area that was exposed to complex organic-bearing fluids with varied temperatures, pressures and compositions over time scales of hundreds of millions of years. We compare the scale and duration of individual surface-mediated chemical reactions to the scales of planetary processes to estimate how many physical/chemical ‘experiments’, each a surface-mediated reaction, might occur on Earth-like worlds.
(a). On the roles of minerals in the origins of life
The probable roles of mineral surfaces in protecting, selecting, concentrating, templating and catalysing reactions of prebiotic organic molecules are recurrent themes in discussions of life's origins. Since the pioneering suggestions of J. D. Bernal [32] and Victor Goldschmidt [33], who independently speculated on the possible influences of a variety of minerals in the origins of life, dozens of authors have proposed general principles and detailed scenarios for mineral-mediated biogenesis [5,7–9,34–37].
Among the specific mineral groups that have been invoked, the clay minerals are among the most frequently cited [34,38–49]. Varied transition metal (e.g. Fe, Ni, Co and Cu) sulfide minerals are also often proposed as playing key catalytic roles in biosynthesis [50–67]. However, many other minerals have also been proposed, including quartz [68–71], feldspar [72–74], zeolite [72,74], olivine [75,76], rutile [77,78], ferrous metal alloys [79], phosphides [80], hydroxides [81–83], hydroxylapatite [84–86], carbonates [87] and borates [88,89].
An important related consideration is the question of what minerals were present on the Hadean Earth [90–93]. If a mineral species was rare or lacking, then it is unlikely to have been a significant contributor to the origins of life. Accordingly, Hazen [93] inventoried 420 mineral species likely to have been present in Earth's near-surface environment at the time of life's origins. This variety of mineral species, each with multiple crystallographic surface topologies [94–96], adds to the potential combinatorial chemical richness of Earth.
(b). Estimation of prebiotic chemical reactions on Earth
The analysis of Earth's combinatorial richness, defined here by the number of surface-mediated organic chemical reactions that might have occurred on the prebiotic Earth, requires the semi-quantitative estimate of four parameters: (i) Individual reaction times or turnover rates, t, and (ii) surface areas, a, for individual organic reactions on mineral surfaces are estimated from the surface chemistry and catalysis literature [11,97]. At the planetary scale, we need to estimate (iii) the time, T, Earth had prior to the emergence of life and (iv) the total reactive surface area, A, of minerals at or near the atmosphere and hydrosphere. The number of prebiotic reactions on Earth, R, is thus the total time and mineral surface area of prebiotic Earth, divided by the time and surface area of an average surface reaction:
This analysis, though semi-quantitative, is designed to underscore our contention that chemical reactions that might require an unusually exacting combination of physical and chemical conditions, and thus be extremely unlikely to be replicated at the spatial and temporal scales of a laboratory environment, may, nevertheless, be all but inevitable in complexly varied chemical and physical environments at planetary scales.
(c). Parameter 1. The time scale of mineral surface reactions, t
Surface-mediated chemical reactions vary widely in their reaction times; no single value can capture the complexities of temperature-dependent catalytic turnover rates, surface dissolution and re-precipitation, passivation by inert molecular species, stirring, and other chemical and physical phenomena that will influence the average time scale of surface-mediated chemical reactions. Nevertheless, experimental studies shed light on typical reaction rates, measured for example in mol cm−2 s−1. In the case of a catalytic reaction at a well-defined surface site, reaction rates are commonly reported as a turnover frequency (TOF) in s−1 [97]. Turnover frequencies vary widely. Values for some enzymes exceed 106 per second [98,99], though more typical TOFs for industrial processes are 102 to 10−2 per second [100].
Recent studies of molecular adsorption/desorption reactions on mineral surfaces, while not directly measuring TOFs, also shed light on these reaction rates. For example, we find that amino acids, sugars and nucleosides exposed to rutile (TiO2), brucite (Mg(OH)2) or clay minerals typically approach equilibrium concentrations in 1–6 h [78,101–103]—values that imply turnover rates less than 103 s per active site. Accordingly, we suggest a plausible average time, t, for prebiotic organic reactions on mineral surfaces:
(d). Parameter 2. The area of a mineral surface reaction, a
The mineral surface area required to mediate an organic chemical reaction is governed primarily by the size of the molecules undergoing reactions. Amino acids, for example, are typically of the order of 1 nm in maximum dimension, whereas membrane-forming phospholipids are approximately 2 nm in length. A conservative estimate of a surface reaction, therefore, is
(e). Parameter 3. The time scale of Earth, T
Radiometric measurements of meteorites constrain Earth's formation to approximately 4.55 billion years ago, with a globe-sterilizing Moon-forming impact prior to 4.4 billion years. Life emerged between that early Hadean period and the early Archaean Eon, when unambiguous fossils of stromatolites—mineralized structures precipitated by microbes—have been documented from 3.7-billion-year-old rocks from Greenland [104]. We conclude that Earth had at least 600 million years, or approximately 2 × 1016 s, during which to conduct origins chemical reactions:
(f). Parameter 4. The reactive mineral surface area of Earth, A
Calculation of Earth's total accessible reactive mineral surface area is fraught with difficulty. Nevertheless, approximations can be made based on observations of modern near-surface environments and calculations of Archaean weathering reactions. Two principal factors determine the reactive area of rocks and minerals in Earth's near-surface environment: (i) the volume, V, of Earth's near-surface minerals in cm3; and (ii) the surface areas of those minerals, M, in cm2/cm3. Thus, A = V × M.
To estimate the volume of near-surface reactive minerals, we multiply Earth's total surface area (approx. 5 × 1018 cm2) by the average depth of Earth's veneer of clay-dominated, fine-grained sediments produced by mechanical and chemical weathering, as well as volcanic ash falls. Sediment depths in modern oceans average 400 m [105–107], whereas terrestrial soils average approximately 15 m in thickness [108,109] (see http://webmap.ornl.gov/wcsdown/wcsdown.jsp?dg_id=1304_1).
A direct comparison of modern and late Hadean/early Archaean sediment volumes is not possible. Earth's Hadean crust and early Archaean crust were probably dominated by mafic and ultramafic igneous rocks, notably basalt and komatiite, with lesser amounts of granitic rocks in the tonalite–trondhjemite–granodiorite (TTG) series [110,111]. Models of Archaean basalt weathering [112] suggest that clay minerals, including kaolinite and Fe2+-smectite, dominate the products in a reducing, slightly acidic aqueous environment. These mineral products, combined with a presumably greater volume of volcanic ash than today, point to significant surface deposits of nanoscale minerals. Assuming a conservative global average thickness of clay-rich sediments of approximately 10 m (=103 cm), the total volume, V, of near-surface deposits with reactive mineral surfaces could have exceeded
Earth's total reactive area of near-surface minerals, M, arises from a variety of sediments, but clay minerals would have been predominant. Clay minerals typically have surface areas of (1–3) × 106 cm2 (roughly the size of a tennis court) per cubic centimetre [113–115]. Therefore, we assume
Consequently, we estimate the reactive mineral surface area of the late Hadean Earth:
(g). How many ‘origins experiments’ can occur on an Earth-like planet?
The four parameters derived above are sufficient to estimate the number of mineral-mediated surface reactions, R, that might have occurred on Earth leading to life's origins:
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4. Conclusion
Chance versus necessity is a misleading dichotomy. Even if estimates of the four relevant parameters described above are in error by a few orders of magnitude, the implications of Earth's combinatorial chemical richness are clear: chemical reactions that are improbable to reproduce at the short time scale and limited spatial dimensions of laboratory experiments—experiments, for example, requiring exacting physical and chemical conditions or unusual juxtaposition of several reactant molecules on an uncommon mineral surface—may be inevitable under the diverse physical and chemical environments possible at planetary scales of space and time.
Strategies exist to increase the likelihood of observing improbable chemical reactions in the laboratory. One can work backwards from modern biochemistry to focus on key molecular species and their products. New approaches in combinatorial chemistry, coupled with computational chemistry, hold the promise of quickly narrowing the search. And chemical and physical intuition will continue to play central roles in origins research. Nevertheless, if elucidation of the origins of life depends on a finicky reaction that occurs under narrow environmental conditions on an Earth-like planet only once in 1050 surface-mediated molecular interactions, then a detailed understanding of origins chemistry may be beyond current laboratory capabilities, even while life's origins is an inevitable feature of warm, wet terrestrial worlds.
Acknowledgements
I am grateful to Carol Cleland for her detailed review and invaluable substantive comments and suggestions. George Cody, Robert Downs, Edward Grew, Grethe Hystad, Harold Morowitz, Shaunna Morrison, Eric Smith and three anonymous reviewers also provided useful discussions and insights.
Data accessibility
This article has no additional data.
Competing interests
I declare I have no competing interests.
Funding
Studies in chance, necessity and the origins of life are supported by a generous grant from the John Templeton Foundation. Additional funding for studies in mineral evolution, mineral ecology, and the coevolution of the geosphere and biosphere were provided by the W.M. Keck Foundation, the Alfred P. Sloan Foundation, the Simons Foundation, the Deep Carbon Observatory, a private foundation, and the Carnegie Institution for Science.
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