PREBIOTIC REACTIONS IN THE BUBBLE THAT WAS FORMED IN CARBONATED
WATER BY IRON ATOMSShinji Karasawa
Miyagi National College of Technology, Professor emeritus, 1-3-6 Oyama, Natori-shi, Miyagi-ken,
Zip code 981-1233, Japan
Fax: 022-382-1879, E-mail: shinji-karasawa@kbh.biglobe.ne.jp(Received: September 1, 2014, Accepted: September 24, 2014)
fine powder of iron is dissolved [6]. But it had
been written without consideration ofintermolecular bonding effects. In this paper,
thestudyon
theorganizationof
intermolecular bonding basing on theobservation on the bubbles that is formed in
the carbonated water by powder of iron isreported.

Abstract
The bubbles are observed by mixing of fine powderof iron into carbonated water. Large bubble formed
from the small bubbles by unification. It carries thefine powder of iron to the surface of water. The
bubble at surface of water will burst, and the debris
will sink to bottom. Robustness of the bubble
increases after repetition of creation and destruction.
These bubbles are generated after a few hours fromthe mixing, but those are not generated after a week.
The measured value of pH (acidity) indicates that thebubbles are suitable for the existence ofhydrogen-carbonate (HCO3-). It is considered thatthe membrane of the bubble is formed byintermolecular binding force between HCO3- andFe2+. The membrane is able to accumulate molecules
selectively in order to form an organization ofmolecules. It might have been functioned as aplatform of chemical evolution, because theultraviolet light in the early earth is able to provide
the energy to cause chemical reactions.

2. Observations of bubbles that are formed incarbonated water by mixing of iron powder
2.1 Experimental procedures
After mixing fine powder of iron into thecarbonated water, the glass container was sealed inorder to hold the carbon oxide gas in the bottle. Theobservations of bubbles were carried out from theoutside of the sealed glass container. Most ofphotographs were taken by digital camera PENTAX
Optio W 90. The close-up photos were taken in
microscope mode with LED 3 point lighting.
The materials used for observations were prepared
as follows. The carbonated water was provided byJapanese Consumers’ Co-operative Union as purecarbonated water but it included only very small
amount (13 ppm) of sodium. Nearly the same results
were observed by using the carbonated water thatwas produced from tap water mixed with dry ice.
The iron powder [the grain size is about 50
microns (meshed #300), and the purity is Fe 90% ormore.] was produced by Kyowa Pure Chemicals
Industry Co. (We can get by mail-order of internet.)
Even by addition of steel wool, similar floating
materials were observed on surface of the carbonatedwater made by tap water mixed with dry ice (CO2)[6].
The purity of materials for the experiment isrequired to ensure experimental reproducibility. But
every material includes impurities in fact. The
repeatability of this description will be guaranteed by
the common characteristics obtained in manydifferent experiments. The other several of results forthe evidences are able to be obtained at the website of[7].

(Keywords) carbonated water, intermolecularinteraction, bubble, membrane, ferrous bicarbonate,metabolism, chemical evolution, BIF
1. Introduction
Observations on the bubbles made from thecarbonated water with fine powder of iron arereported in this article. Although the bubble isobservable, it is difficult to decide the structure. The
membrane of a bubble is formed by intermolecularbonding force among ions at the interface of theliquid. The system of molecules is able to accumulate
molecules. The intermolecular interaction would givea step for chemical reactions. The bubble could berepaired by mechanism of the production. It is aself-sustained organization of molecules. It wasconsidered that the bubble is a prime candidate forthe origin of life.
Many scientists have been interested in the originof life [1]. After proposal on the origin of life by A. I.
Oparin, many models have been proposed [2,3]. But,
the detailed mechanism to form the organization ofintermolecular bonding force has not been discussed.
Z. Borowska & D. Mauzerall reported theformation of organic molecule caused by reduction ofcarbon dioxide (CO2(aq)) under the condition ofirradiating aqueous ferrous ion (Fe2+) at neutral pHwith near-UV light (306-390 nm) [4,5]. However,there is no report of study on the bubble that wasformed by means of intermolecular bond amongpolyatomic ions of HCO3-.
S. Karasawa (2010) had reported that bubbles
are made from the carbonated water in which

Viva Origino 42 (2014) 12 - 17
© 2014 by SSOEL Japan

2.2 The adhering of iron particles to a block of dryice (CO2(s)) in liquid water
By mixing fine powder of iron into the carbonatedwater, we can observe the phenomena shown in
Fig.1.
A block of dry ice (CO2(s)) in water collects thefine powder of iron. There is Brownian motion ofpowder of iron. Thermal motion of cluster of water isable to change the position of very fine powder ofiron in water. The adhering indicates the existence ofa long-range force between carbon dioxide and12

Viva Origino 42 (2014) 12 - 17

powder of iron in the water. Generally speaking,every atom has the adaptability to its circumstance.
The metabolism is supported by the long-range force
and thermal motion.	  The most of intermolecular bonding structure will
be decomposed by the thermal motion of molecule.
But, the thermal motion is suppressed in someinterconnected molecules. So, decomposition ofintermolecular bonding material will be suppressedby the interconnection. The intermolecular bonding
material will be changed into compound by theenergy given from outer world such as the irradiationof ultra violet light.

2.4 A primitive metabolism that is observed in bubble
Intermolecular bond in the membrane of bubble isdifferent from that of inside of liquid water. Theintermolecular binding force at the interface isemphasized by regular alignment of molecules. In abubble, the molecules of membrane form a cage
structure of molecules.
The shape of bubble responds to external andinternal changes. The membrane of a bubble isflexible. The flexibility is caused by weakintermolecular binding force. Although the bubble isrobust against shaking the water, it is easily broken
by stopping the shaking [8]. The process of repair isthe same to the production. The long life of bubble isyielded under the condition of production. The
continuous renewing will achieve the long life. Thisphenomenon indicates the origin of metabolism.
The metabolism is carried out by the adaptabilityof electronic structure of atom and together with theintermolecular force among the neighboring atoms.
Here, neighboring atoms will be exchanged bythermal motion of molecules in the substances. Theorganization of molecules will be changed by theresult of reaction. The renewed environment
produces renewed products.

Fig.1 Fine powder of iron (Fe) adhered to the block of dry
ice (CO2) in carbonated water. The right bottle includes
the iron powder of meshed #300. The left bottle includes
the iron powder of meshed #200.

3. Analyses on the substance of the bubble
3.1 Observations of dried bubbles
It is difficult to analyze the state of bubble. The
sample to be analyzed was dried. We can see thedried bubbles at the upper wall of the glass bottle asshown in Fig.3. We can recognize two types of

2.3 The bubble that was formed in carbonated waterby iron particles
The membrane of bubble that includes withparticles is produced by mixing iron powders incarbonated water as shown in Fig.2.
At first, molecules of carbon dioxide in thecarbonated water are gathered by adhering at thesurface of iron (Fe). After that, small bubbles aregenerated at surface of the iron powder. The fineparticles of iron are incorporated in the membrane ofbubble. After a while, the small bubbles become bigby coalescing with each other. The big bubble is able
to rise with fine particle of iron to surface of water.
The floating material at the surface is a thin plane.
It escapes from a spoon of stainless steel. It isexplained that the floating material includes Fe2+ions.

Fig.3 The dried bubbles that had been adhered tothe wall of the glass.	  	 Fi.g. 4 (a) Dried floating materials. (b) Membrane ona wall. Fig.4 (a) is the photo on the dried floating
materials made from carbonated water and steel wool.
Fig.4 (b) is the photo on the membrane that was formedby adhering to the wall of the glass in 90 cc ofcarbonated water mixed with 5 g of #300 iron powders.

Fig.2 Bubbles that were generated in the carbonatedwater (saturated solution 75 cc) that had been mixed
with fine powder (#300) of iron (5 g). This photograph
was taken after 75 hours from mixing.

13Viva Origino 42 (2014) 12 - 17

substances in Fig.3. One is black particle made ofiron powder. The other is yellow membrane oftransparency.	  Fig.4 (a) is photograph of dried specimen on alaboratory dish. On the other hand, a structural color
is observed on glass wall. The membrane has been
formed adhering to the glass wall. Fig.4 (b) wasphotographed after 5 months from mixing iron andcarbonated water. The sample (b) was irradiated byultraviolet light during a few days at beginning of theperiod of 5 months.
3.2 Inspections by Fourier Transform Infrared
Spectroscopy (FT-IR)

Fig.6 In case of the sample that is covered with Au
coating, a large amount of oxygen is detected by X-ray
spectrometry (EDS) of a scanning electron microscopy(SEM).

4. The mechanism that forms bubbles incarbonated water by iron atom
4.1 Changes of pH value on the water (75 cc) under
the atmosphere of 1 atm of 100% CO2
When CO2 gas dissolves in water, 3 different
forms can occur i.e. H2CO3(aq), HCO3-(aq) and CO32-(aq)(p.107, Fig.19 [9]). Activities of those species in thecarbonated system are given by Drever (1988). Major
species in the carbonated water is divided into
following 3 regions (p.224 [10]).
H2CO3 < pH=6.35 < HCO3- < pH=10.33 < CO32-Fig.5 An example of FT-IR data on the dried
membrane of bubble.

The value of electrolytic dissociation constant of issmall. So, the most of dissolved carbon dioxides are
the form of molecules. The reactions are as follows.

FT-IR on the dried membrane of bubble wasmeasured [6]. A new example of data is shown in
Fig.5. But, it is difficult to clarify the meaning of thepeak from this data, because the confirmed referable
data on such materials do not exist. At this point, it isdifficult to decide the weak structure of themembrane of bubble by FT-IR. The accumulation ofmany kinds of data will contribute to decide thestructure in the future.

KCO2 = 10-1.47
CO2(aq) + H2O ⇔ H2CO3(aq) ;+H2CO3(aq) ⇔ HCO3 (aq) + H (aq) ; Ka1 = 10-6.35
HCO3-(aq) ⇔ CO32-(aq) + H+(aq) ;Ka2 = 10-10.33

(1)
(2)
(3)

The values of equilibrium constants for thecarbonate system are for fresh water at 25oC from(p.221 [10]). The reactions Eq.(2) and Eq.(3) producehydrogen ion (H+(aq)). An amount of the hydrogen ion
in natural water mainly depends on the reaction ofEq.(2).
The value of pH on the water is changed (Fig.7),
when the atmosphere on surface of water is 100%
CO2, and the pressure is 1 atm. The volume of wateris 75 cc in a vessel of 100 cc with cross section of 30cm2.
The available hydrogen ions are increased bydissolved carbon dioxides. The increase of hydrogenion will lower the value of pH. But, the hydrogen ion
in aqueous solution becomes associated with an
oxygen atom in the water.

3.3 Inspections by energy dispersive X-ray
spectrometry of scanning electron microscopy
The dried membrane of the bubble was inspectedby energy dispersive X-ray spectrometry (EDS) of
scanning electron microscopy [6]. The substancecontains atoms of carbon (C), oxygen (O) and iron(Fe). Here, the hydrogen (H) does not appear in thisEDS analysis. As the result of existence of ironparticle, the ratio among these elements differs by theposition of analysis.
A large peak of oxygen atom (O) is detected incase of the sample of which surface is covered withAu coating (Fig.6). But in the sample that did notcoating of Au, the amount of oxygen remarkably
decreases. The facts indicate that the membrane will
be contained with many H2O molecules.

14Viva Origino 42 (2014) 12 - 17

Fig.9 The molecular model of Fe(HCO3)2(aq) thatindicates the forming of CO 2(g) by mixing fine powderof iron into the carbonated water.

Fig.7 Changes of pH value on the water (75 cc) under
the atmosphere of 1 atm of 100% CO2.

4.2 Changes of alkalinity of the carbonated water by
mixing of fine powder of iron
Fine powder of iron dissolves slowly in thecarbonated water. The hydrogen ions in carbonatedwater are decreased by the iron ion. The measured
values of pH increase along the time progress asshown in Fig.8.
These results are the evidences of indication that
HCO3- is effects to form the inorganic bubble.

Fig.10 A molecular model of membrane by Fe(HCO3)2(aq).
The positioning of atoms in Fig.10 is nearly the same toFig.9. The polyatomic ion of the HCO3-(aq) that makes
hydrogen bonds attaches to an iron atom.

plane triangle structure of 3 oxygen atoms equivalentjoined around one carbon atom. The paralleling lineof hydrogen bond of carbonic acid ions HCO3- isconnected by iron (Fe2+) atom two-dimensionally.
This structure is able to explain the mechanism of
proton motive force, because the movement ofhydrogen bond accompanies with that of thedeformation.
Generally speaking, the iron atom is able to form acomplex. It is organized by d-electron of the iron ion.
The membrane of Fe(HCO3) is able to accumulate
molecules selectively in order to form anorganization of molecules.

Fig.8 Changes of pH value on carbonated water (75cc) after mixed with powder of iron (#300, 5 g)

4.3 The model that produces bubbles in thecarbonated water by mixing of powder of iron
When Fe atom connects with OH-(aq), theconnection forms a unit of Fe(OH)2. In this case, themolecule of CO2 will gather and it is able to produce
gas of CO2 as illustrated in Fig.9.
4.4 The model that produces membrane in thecarbonated water by mixing of powder of iron
Another units of planer structure of Fe(HCO3)2(aq)is illustrated in Fig.10. The positioning of atoms inFig.10 is nearly the same to Fig.9. There areintermolecular bonds between an ion of iron (Fe2+)
and polyatomic ions of HCO3-(aq) (Fig.10).

5. Effects of bubbles on geochemistry in the EarlyEarth
5.1 The oldest microbial mats and BIF
M. M. Tice & D. R. Lowe reported the oldest
microbial mats and banded iron formations (BIF)

Each carbonic acid (CO32-) in liquid state takes a15

Viva Origino 42 (2014) 12 - 17

those had formed at 3.416 billion years ago in Buck
Reef Chert, South Africa [11]. The BIF is iron-rich,
but the other metal is low concentration in it. The BIF
at South Africa includes iron carbonate (FeCO3).
FeCO3 was produced in the alkali state of carbonatedwater that was caused by means of addition of iron
ion, i.e., it was produced by dehydrationaccompanying with supply of iron as follows.

emitted by the volcanic eruptions.
The floating material was produced fromcarbonated water with iron. It was oxidized by theenergy that came from outer world. And the ironoxide was deposited at the bottom of sea. That is theformation of BIF.
On the other hand, neighboring atoms incarbonated water with iron are able to exchange bythermal motion [16]. There is the adaptability ofsubstance that is caused by the electronic structure.
Some organic molecules were produced from thefloating substance of intermolecular bonds by theenergy that comes from outer world such as
ultraviolet ray. The molecules will be evolved
through the repetition of production and destruction.
That would be chemical evolution.
The carbon isotope of 12C in liquidity state of
substance can be accumulated in the substances
floated in the early sea, because the motion of 12C ismore active than 13C .
The structure that is formed by Fe(HCO3)2(aq) isable to realize a proton driving force. That is, theweak intermolecular bond by the proton is able tomove together with a deformation of the structure.
Since process of repair is the similar to theproduction, the bubble is self-sustained system. The
bubble is an autonomous system with open-ended
evolutionary capacities. It may satisfy the definitionof life [17], “Life is a self-sustained chemical systemcapable of undergoing Darwinian evolution” (Joyce,1994).

(4)
Fe2+(aq) + 2HCO3-(aq) ⇔ Fe(HCO3)2Fe(HCO3)2⇔ Fe(OH)2 + 2CO2(g)(5)
Fe(HCO3)2 + Fe(OH)2 ⇔ 2FeCO3(s) + 2H2O(aq) (6)There are reports on UV driven photo-oxidation offerrous ions for banded iron formation (BIF)([12-14]). The photo-oxidation of iron atom maygenerate formaldehyde (HCHO) [5] and molecularhydrogen (H2) [15]. These products of thephotoreaction would be able to make membrane of
the robust bubble.
Isotope of 12C is taken easily in the bubble
compared with 13C, because the thermal
motion of atom is required for thephotoreaction. The effect of thermal motion isalso functioned at the photosynthesis that
produces organic molecules.

6. Conclusions
The robust bubbles covered with particle of irons
were generated in the carbonated water after several
hours from mixing of powder of iron. The membraneof bubble is formed by a weak intermolecular bond.
How to decide the delicate molecular structure ofintermolecular bonding state is remained for thefuture work.
Although we cannot directly analyze those bubbles,
we can estimate the model of consistent structurefrom many evidences. That is, each Fe2+ issurrounded by 4 pieces of HCO3- ions. There arehydrogen bonds between HCO3- ions. So, Fe(HCO3)2
forms a planer structure, and it forms membrane ofthe bubble. Moreover, the structure of Fe(HCO3)2(aq)has advantages to induce chemical reactions. It isable to operate the primitive metabolism.
The bubble can be functioned as a platform ofprebiotic reaction. The intermolecular reactions atlong period in the early earth had effected to thesubstances on the earth. It is possible to contribute to
explain about the formation of oldest organic carbonand BIF.
The proposing model on the bubble of weakintermolecular bonds in liquid water between the ironatom and polyatomic ions of HCO3- is a start for themolecular study of the chemical evolution.

Fig.11 An illustration on the formation of microbial
mats at 3.42 billion years ago in Buck Reef Chart inSouth Africa [11].

Fig.11 is an illustration of the above mentioned
mechanism of BIF and microbial mats.
5.2 The scenario of the bubble related with theformation of oldest organic carbon
The facilities for production and the products arepresent at the same time. So, the production of theoldest organic carbon from inorganic matter is likely
to occur simultaneously with the birth of organism.
However, the production of the oldest organic
molecule by means of the photosynthesis is difficult,because a complicate system of organic molecules isnecessary for the photosynthesis.
The following story can be postulated. At about
3.5 billion years ago, temperature of seawater becamemild from hot temperature. The carbon dioxide in theatmosphere was dissolved in the water at lowertemperature. At the same period, iron particles were16

Viva Origino 42 (2014) 12 - 17

Acknowledgements
The author would like to thank to Prof.
YAMAGISHI, Akihiko, Tokyo University of
Pharmacy and Life Science; Prof. KAKEGAWA,
Takeshi, Graduate School of Science, Tohoku
University, and Prof. MARUYAMA, Shigenori,
Earth-Life Science Institute, Tokyo Institute ofTechnology who gave him useful suggestions.
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