A POSSIBLE RELATIONSHIP BEWTEEN THE GREAT OXIDATION EVENT AND
THE PALEOPROTEROZOIC SNOWBALL EARTH EVENTEiichi Tajika1* and Mariko Harada2
1Department of Earth and Planetary Science, Graduate School of Science, The University ofTokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan2
Department of Molecular Biology, Tokyo University of Pharmacy and Life Science, 1432-1
Horinouchi, Hachioji, Tokyo, 192-0392, Japan*Corresponding author: Department of Earth and Planetary Science, Graduate School ofScience, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japanemail: tajika@eps.s.u-tokyo.ac.jp(Received: 17, September, 2017 Acceted: 10, October, 2017)has been a matter of debate, it should haveappeared, at least, before the GOE, probably morethan several hundred million years before the GOE[e.g., 4-6].
As seen in the stratigraphy of the Transvaal
Supergroup in the Griqualand West region in South
Africa, iron and manganese (Mn) bearing units ofthe Hotazel Formation, the first large-scale
sedimentary Mn ore deposits in the Earth’s history,
have been formed just after the Makganyenesnowball Earth event (global glaciation) at ~2.2 Ga(Fig. 2) [7, 8]. Because Mn has a high oxidation
potential, which cannot be oxidized virtually
without O2, it is suggested that this would be an
evidence for the rise of O2 just after theMakganyene snowball Earth event [8].
In this paper, a hypothesis on this issue
proposed recently [9] will be reviewed, and apossible relationship between the snowball Earthevent and the rises of O2 will be discussed.

Abstract
Recent progresses of studies on the rise of
atmospheric oxygen during 2.4-2.1 billion years
ago (the Great Oxidation Event), the Paleoproterozoic snowball Earth event occurred 2.3-2.2
billion years ago, and a possible relationshipbetween them are reviewed and discussed.
Formation of manganese ore deposits at 2.2 billion
years ago suggests that the rise of oxygen may haveoccurred just after the Paleoproterozoic snowball
Earth event and, also, an overshoot of theatmospheric oxygen level is suggested to haveoccurred 2.2-2.1 billion years ago. Numericalresults with a coupled model of biogeochemical
cycle, photochemical reactions, and hydrogenescape to space shows that an extremely hot
climate in the aftermath of the snowball Earthevents causes unusually high primary productivity
in the ocean through intensive chemical
weathering, which results in a transition of theatmospheric oxygen levels from low to high stablesteady-states, with an extensive and long-lastingovershoot. Thus, the rise of oxygen should haverequired perturbation to the system which made theoxygen production rate one order of magnitude
higher than the normal rate. Such an extremely
large perturbation could have been caused only by
the snowball Earth event.
Keywords: oxygen, Great Oxidation Event,snowball Earth, cyanobacteria
1.

Introduction
A rise of oxygen (O2) in the atmosphere may
be one of the most critical factors for the evolutionof life during the Earth's history. The concentrationof O2 in the atmosphere is 20.9% at present, while
there would have been little O2 in the atmosphereof early Earth. As shown in Fig. 1, the atmosphericlevels of O2 would have risen from < 10-5 of thepresent atmospheric level (PAL) to 10-2-10-3 PAL,
sometime between 2.4 and 2.1 billion years ago(Ga) [e.g., 1]. This episode is called the "Great
Oxidation Event" or GOE [e.g., 1-3].
Oxygenic photosynthesis due to cyanobacteria
would have been responsible for the GOE.
Although the age of emergence of cyanobacteria

Viva Origino 2017, 45, 5© 2017 by SSOEL Japan

Fig. 1 The history of O2 in the atmosphere. Theatmospheric O2 levels would have risen mainly inthe two periods: the Great Oxidation Event (GOE)
during 2.4-2.1 Ga and the Neoproterozoic
Oxidation Event (NOE) during 0.8-0.6 Ga [e.g., 1].
An overshoot of O2 may have occurred in 2.2-2.1
Ga [e.g., 14-16]. Arrows with filled circles and bars
are constraints from geochemical studies.

2.

Stability of atmospheric oxygen levels
There seems a time gap between the emergenceof cyanobacteria which produces O2 and the rise of1

Viva Origino 2017, 45, 5

O2 in the atmosphere (i.e., GOE) as described in
the previous section. The levels of the atmospheric
O2 were stable below 10-5 PAL before the GOE (>2.4 Ga) [10. 11]. The O2 levels would have beenstable around 10-2-10-3 PAL between the GOE andanother oxygen-rise event occurred 0.8-0.6 Ga(called the “Neoproterozoic Oxidation Event” orNOE) [1, 12], and also stable around 1 PAL after
the NOE (~during the Phanerozoic) (Fig. 1).
Because a residence time of O2 in the atmosphereis on the order of 106 years during the Phanerozoic,
the stability of the atmospheric O2 levels on theorder of 108 years cannot be explained withoutsome unknown negative feedback mechanisms
which stabilize the atmospheric O2 levels. Thereseems to be multiple (at least, three) stable levelsof the atmospheric O2, and the rises of O2 in theGOE and the NOE could have corresponded totransitions between those stable levels [e.g., 13].
Goldblatt et al. (2006) [13] proposed a model
which explains bistability of atmospheric O2 levels(i.e., a model with two stable O2 levels); one is low(10-5 PAL) and the other is high (10-2 PAL)
atmospheric O2 levels [13]. This is derived from anonlinear increase in the lifetime of atmosphericO2 due to production of ozone from O2 in theatmosphere. The ozone shields troposphere fromultraviolet (UV) flux from the Sun, because UV
flux promotes oxidation of CH4 which consumes
O2 at last, once the O2 level exceeds 10-5 PAL [13].
It is however difficult for the atmospheric O2 levels
to make a transition from low to high stable steadystates without unusually large perturbations to acarbon biogeochemical cycle system. Therefore, it
could have been possible that the low O2 levels(<10-5 PAL) have persisted for several hundred
million years after the emergence of oxygenic
photosynthesis. The reason for the transition of theatmospheric O2 levels during the GOE is either bya significant increase in oxygen input from thebiosphere or by a decrease in reductant input from
Earth’s interior [e.g., 13]. However, the actual
mechanism to cause the changes has not been clear.
Recent discoveries of geochemical evidence
for dee-water oxygenation at 2.1 Ga in theFrancevillian Groupe, the Republic of Gabon [14],and of the global deposition of sulfate minerals at
2.2-2.1 Ga [15, 16] suggest that the O2 levels may
have risen more dynamically with an intensive
overshoot, up to ~0.1-1 PAL and lasting for ~108years (Fig. 1) [1, 15]. Such a dynamical behavior
should provide strong constraints on a mechanismand magnitude of reduction-oxidization (redox)
budget change during the GOE. Also, it isinteresting to note that the rise of O2 seems to haveoccurred just after a snowball Earth event (globalglaciations), as described below. Hence, there
might have been causal relationship between them.

3.

Rise of atmospheric oxygen triggered bysnowball Earth event
We proposed a possible mechanism for the riseof O2 with an intensive overshoot, which would
have occurred inevitably as a result of terminationof the snowball Earth event [9].
As shown in Fig. 2, a massive deposition ofMn-oxides in the Hotazel Formation occurs justafter a deposition of glacial sediments of theMakganyene Diamictite Formation. The glacial
diamictite is overlain by volcanic lavas of theOngeluk Formation from which an age of 2.222±0.013 Ga and a paleolatitude of 11±5o are reported,
providing an evidence for low-latitude glaciations,that is, a snowball Earth event [7, 8].
In the snowball (globally ice-covered) climate,
the globally- and annually-averaged surface
temperature (hereafter, just describes the surfacetemperature) becomes -40oC, hence all the surface
water should freeze completely, which enables
volcanic CO2 to accumulate in the atmosphere until
the ice melts [17]. A 0.7 bar of CO2 is required toaccumulate to melt the surface ice at 2.2 Ga whenluminosity of the Sun was probably 83% of that atpresent [18, 19]. After the melting of ice, thesurface temperature becomes 60oC because ofstrong greenhouse effect of 0.7 bar of CO2 (Fig. 3)

Fig.2 Stratigraphy of the Transvaal Supergroup inSouth Africa. Glacial sediments of the Makganyene
Diamictite Formation (corresponding to the
Paleoproterozoic snowball Earth event) is overlain
by the Hotazel Formation (Fe-Mn ore deposits),with lava flows of the Ongeluk Formation between
them. Oxidation of Fe and Mn owing to a rise of O2
is suggested to have occurred just after the
Paleoproterozoic snowball Earth event, at around
2.2 Ga.

2Viva Origino 2017, 45, 5

The standard results of variations of pCO2, thesurface temperature, chemical weathering rate ofsilicate minerals, concentration of dissolved
phosphate in surface water ([PO4]), burial rate oforganic carbon (which is equivalent to a net
production rate of O2), and precipitation rate ofcarbonate are shown in Figs. 4. The surface
temperature decreases with time, but unusually hot
climate (>300 K) continues on the order of 105
years (Fig. 4b). Because of the dependency of[19, 20]. Intense chemical weathering ofcontinental rocks occurs owing to its temperaturedependency, which results in a drawdown of CO2
through precipitation of carbonate minerals in theoceans [e.g., 20]. Chemical weathering would
deliver a large quantity of bio-limiting nutrients,
such as phosphorus, from the continents to theoceans, resulting in blooming of cyanobacteria toproduce a large amount of O2 to the atmosphere.
We modeled a coupled system of atmosphericphotochemistry-climate-biogeochemical cycles tounderstand theoretical consequence of terminationof the Paleoproterozoic snowball Earth event
which may have caused the rise of O2 in theatmosphere [9]. The model includes a redox
balance model of Goldblatt et al (2006) [13].
Processes considered are production of O2 andmethane (CH4) from marine biosphere,
photochemical oxidation of CH4 in the atmosphere,hydrogen escape to space, chemical weathering ofsilicate and carbonate minerals on the continents,oxidative weathering of organic matters on thecontinents, precipitation of carbonate and burial oforganic matters on seafloor, and reductant input tothe surface from Earth’s interior. Primary
productivity, that is, oxygenic photosynthesis ofcyanobacteria is assumed to be limited byphosphorus delivered from the continents to theoceans through chemical weathering.

Fig. 3 Schematic variations of the surface temperatureduring the snowball Earth event. The surface
temperature becomes up to 60oC just after thedeglaciation, because 0.7 bars of CO2 should
accumulate in the atmosphere via volcanism until
melting of surface ice [e.g., 18, 19].

Fig. 4 Numerical results of variations of each variable after the termination of the snowball Earth event [9]. (a)pCO2, (b) global surface temperature, (c) chemical weathering rate of silicates, (d) phosphate concentration in deep
seawater, (e) burial rate of organic carbon (i.e., net production rate of O2), and (f) carbonate precipitation rate.

3Viva Origino 2017, 45, 5Fig. 5 The numerical results of variations of the atmospheric O2 levels after the termination of the snowball Earthevent [9]. (a) Evolutionary track of the atmospheric O2 levels superimposed on a bistability diagram between O2
levels and net primary productivity by Goldblatt et al. (2006) [13]. (b) Time variations of O2 levels.

levels to have risen to such a very high levels as
seen today. The rise of O2 requires large-scale
perturbation to the system which causes the O2
production rate to increase one order of magnitude
higher than the normal rate. Such an unusuallylarge perturbation could have been caused only bysnowball Earth events. In this context, it issuggested that the Paleoproterozoic snowball Earthevent has inevitably resulted in the rise of O2 withan overshoot, which may have promoted biologicalevolution toward the prosperity of oxygendependent life.

chemical weathering reactions on temperature, therate of chemical weathering of silicate minerals
also remains much (ca. 20 times) higher than thepresent level on the order of 105 years (Fig. 4c). As
a result, a large quantity of phosphates is delivered
to the oceans, enhancing [PO4] 10 times higher
than the present level on the order of 104 years (onthe timescale of mean residence time of phosphatein the ocean) (Fig. 4d). It results in an increase in
primary productivity of cyanobacteria (henceburial rate of organic carbon; Fig. 4e) 10 times
higher than the present level. Burial rate of organiccarbon is equivalent to a net production rate of O2,
hence the atmospheric O2 levels should increase
greatly (Fig. 5).
Transition from low to high stable steady-statesof the atmospheric O2 levels occurs owing to anincrease in a net production rate of O2 one order ofmagnitude higher than the normal levels (Fig. 5).
Interestingly, the O2 level increases up to 1 PAL in
106-107 years after the termination of the snowball
Earth event, and, then, decreases to 0.01 PAL,
taking a timescale on the order of 108 years,
representing an overshoot of O2 levels (Fig. 5).
The overshoot of the atmospheric O2 levels
occurs because the primary productivity becomes
one order of magnitude higher than the normal
level for a timescale on the order of ~105 years.
Such an exceptionally large perturbation to thecarbon biogeochemical cycle system cannot occur
usually, but can occur after the termination ofsnowball Earth events (see [9] for more details).

Acknowledgments
This study was partially supported by a Grant-inAid for Scientific Research from the Japan Society
for Promotion of Science (KAKENHI GrantNumber 16K05618).
References
1. Lyons, T.W., Reinhard, C.T. and Planavsky, N.J. The rise ofoxygen in Earth’s early ocean and atmosphere, Nature 506,307–315 (2014)
2. Holland, H. D. Volcanic gases, black smokers, and the Great
Oxidation Event, Geochim. Cosmochim. Acta 66, 3811–3826 (2002)
3. Holland, H. D. The oxygenation of the atmosphere andoceans, Phil. Trans. R. Soc. B 361, 903–915 (2006)
4. Crowe SA, Dossing LN, Beukes NJ, Bau M, Kruger SJ, Frei
R. and Candield, D. E. Atmospheric oxygenation threebillion years ago, Nature 501, 535-538 (2013)
5. Planavsky NJ, Asael D, Hofmann A, Reinhard CT, Lalonde
SV, Knudsen A, Wang, X., Ossa, F., Pecoits, E., Smith, A. J.
B., Beukes, N. J., Bekker, A., Johnson, T. M., Konhauser, K.
O., Lyons, T. W. and Rouxel, O. J. Evidence for oxygenic
photosynthesis half a billion years before the Great
Oxidation Event, Nature Geosci. 7, 283-286 (2014)
6. Mukhopadhyay J, Crowley QG, Ghosh S, Ghosh G,Chakrabarti K, Misra B, Heron, K. and Bose, S.
Oxygenation of the Archean atmosphere: New paleosol
constraints from eastern India, Geology 42, 923-926 (2014)
7. Evans, D.A., Beukes, N.J., and Kirschvink, J.L. Low-latitude
glaciation in the Palae-poproterozoic era, Nature 386, 262‒
266 (1997)
8. Kirschvink, J.L., Gaidos, E.J., Bertani, L.E., Beukes, N.J.,

4.

Conclusion
The atmosphere and ocean contains large
quantity of O2 at present because oxygenic
photosynthesis of life has been producing O2 since
the emergence of cyanobacteria. However, if there
are multiple steady-state levels of O2 in theatmosphere, it is not easy for the atmospheric O24

Viva Origino 2017, 45, 5Gutzmer, J., Maepa, L.N. and Steinberger, R.E.
Paleoproterozoic snowball Earth: Extreme climatic andgeochemical global change and its biological consequences,
Proc. Natl. Acad. Sci. 97, 1400‒1405 (2000)
9. Harada, M., Tajika, E. and Sekine, Y. Transition to anoxygen-rich atmosphere with an extensive overshoottriggered by the Paleoproterozoic snowball Earth, Earth
Planet. Sci. Lett. 419, 178–186 (2015)
10. Farquhar, J., Peters, M., Johnston, D.T., Strauss, H.,
Masterson, A., Wiechert, U. and Kaufman, A.J. Isotopic
evidence for Mesoarchaean anoxia and changing atmospheric sulphur chemistry, Nature 449, 706–709 (2007)
11. Pavlov, A. and Kasting, J. Mass-independent fractionationof sulfur isotopes in Archean Sediments: strong evidence foran anoxic Archean atmosphere, Astrobiology 2, 27–41(2002)
12. Rye, R. and Holland, H.D. Paleosols and the evolution ofatmospheric oxygen: acritical review, Am. J. Sci. 298, 621–672 (1998)
13. Goldblatt C, Lenton T. M, Watson A. J. Bistability ofatmospheric oxygen and the Great Oxidation, Nature 443,683-686 (2006)
14. Canfield, D.E., Ngombi-Pemba, L., Hammarlund, E.U.,
Bengtson, S., Chaussidon, M., Gauthier-Lafaye, F., Meunier,A., Riboulleau, A., Rollion-Bard, C., Rouxel, O., Asael, D.,
Pierson-Wickmann, A.-C. and El Albani, A. Oxygen
dynamics in the aftermath of the Great Oxidation of Earth’satmosphere, Proc. Natl. Acad. Sci. USA 110, 16736–16741(2013)
15. Bekker A. and Holland H. D. Oxygen overshoot andrecovery during the early Paleoproterozoic, Earth andPlanetary Science Letters 317–318, 295-304 (2012)
16. Schroder, S., Bekker, A., Beukes, N. J., Strauss, H. and vanNiekerk, H. S. Rise in seawater sulphate concentration
associated with the Paleoproterozoic positive carbon isotope
excursion: evidence from sulphate evaporates in the ~2.22.1 Gyr shallow-marine Lucknow Formation, South Africa,
Terra Nova 20, 108-117 (2008)
17. Kirschvink, J.L. Late Proterozoic low-latitude global
glaciation: The snowball earth, The Proterozoic Biosphere;
edited by Schopf, J.W. and Klein, C., Cambridge UniversityPress, Cambridge, 51‒52, 1992
18. Caldeira, K. and Kasting, J.F. Susceptibility of the early
Earth to irreversible glaciation caused by carbon dioxide
clouds, Nature 359, 226‒228 (1992)
19. Tajika, E. Faint young Sun and the carbon cycle: Implication
for the Proterozoic global glaciations, Earth Planet. Sci. Lett.
214, 443‒453 (2003)
20. Hoffman, P.F., Kaufman, A.J., Halverson, G.P. and Schrag,D.P. A Neoproterozoic snowball, Earth, Science 281, 1342‒
1346 (1998)

5