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2013-p-04

Space Exposure of Amino Acids and Their Precursors


in the Tanpopo Mission Using the International Space Station
By Kensei Kobayashi1), Hajime Mita2), Hikaru Yabuta3), Kazumichi Nakagawa4), Yukinori Kawamoto1), Kazuhiro Kanda5),
Eiichi Imai6), Hirofumi Hashimoto7), Shin-ichi Yokobori8),
Akihiko Yamagishi8), and Tanpopo WG7)
(5mm)
1)

Yokohama National University, Yokohama, Japan

2)

Fukuoka Institute of Technology, Fukuoka, Japan


3)

Osaka University, Toyonaka, Japany


4)

5)
6)

Nagaoka University of Technology, Nagaoka, Japan


7)

8)

Kobe University, Kobe, Japan

University of Hyogo, Kamigori-cho, Japan


JAXA/ISAS, Sagamihara, Japan

Tokyo University of Pharmacy and Life Science, Hachioji, Japan

A wide variety of organic compounds have been found in space, and their relevance to the origin of life is discussed.
Interplanetary dust particles (IDPs) are most promising carriers of extraterrestrial organic compounds, but presence of
bioorganic compounds are controversial since they are so small and were collected in the terrestrial biosphere. In
addition, IDPs are directly exposed to cosmic and solar radiation. Thus, it is important to evaluate the stability of organics
in IDPs in space environment.
We are planning a novel astrobiology mission named Tanpopo by utilizing the Exposed Facility of Japan Experimental
Module (JEM/EF) of the International Space Station (ISS). Two types of experiments will be done: Capture experiments
and exposure experiments. In the exposure experiments, organics and microbes will be exposed to the space
environments to examine possible alteration of organic compounds and survivability of microbes.
Selected targets for
the exposure experiments of organic compounds are as follows: Amino acids (glycine and isovaline), their possible
precursors (hydantoin and 5-ethyl-5-methyl hydantoin) and complex precursors CAW synthesized from a mixture of
carbon monoxide, ammonia and water by proton irradiation. In addition to them, powder of the Murchison meteorite will
be exposed to examine possible alteration of meteoritic organics in space. We will show the results of preparatory
experiments on ground by using a UV lamp, synchrotron facilities, and a heavy ion irradiation facility.

Key Words: Amino Acid Precursors, Exposure, Origins of Life, Interplanetary Dust Particles, International Space Station

1.

Introduction

Module (JEM-EF) on the International Space Station (ISS).


Two types of experiments will be done in the Tanpopo
Mission: Capture experiments and exposure experiments. In
order to collect cosmic dusts (including IDPs) on the ISS, we
are going to use extra-low density aerogel, since both cosmic
dusts and ISS are moving at 8 km s-1 or over. We have
developed novel aerogel whose density is 0.01 g cm-3. In the
exposure experiments, organics and microbes will be exposed
to the space environments to examine possible alteration of
organic compounds and survivability of microbes. Here we
will report on the selection of organic compounds for the
space exposure, and the results of preparatory experiments on
ground.
A number of amino acids were detected in water extract of
carbonaceous chondrites.
It is controversial whether
meteorites contain free amino acids or amino acid precursors.

It has been reported that a wide variety of organic


compounds are contained in carbonaceous chondrites and in
comets. Their relevance to the emergence of terrestrial life is
widely discussed. It was suggested that more organic
carbons were delivered to the early Earth by interplanetary
dust particles (IDPs) than by meteorites or comets1). IDPs
(or micrometeorites (MMs)) have been collected in ocean
sediments, Antarctic ices, and air in stratosphere. Though
presence of bioorganic compounds in IDPs/MMs is expected,
it is difficult to judge it since they are so small and were
collected in the terrestrial biosphere. Thus it would be of
importance to collect IDPs out of the terrestrial biosphere.
We are planning a novel astrobiology mission named Tanpopo
by utilizing the Exposed Facility of Japan Experimental

When dusts are formed from meteorites or comets in


interplanetary space, they are exposed to high-energy particles
and photons. In order to evaluate stability and possible
alteration of amino acid-related compounds, we chose amino
acids (glycine and isovaline) and hydantoins (precursors of
amino acids), and products of proton irradiation of a mixture
of CO, NH3 and H2O (CAW; containing high molecular
weight precursors of amino acids2)).
We performed ground simulation experiments by using
accelerators (HIMAC, NIRS, Japan and NewSUBARU,
University of Hyogo, Japan), which showed that amino acid
precursors were much more stable than free amino acids
against radiation. The ground simulation also showed that
solar UV is more lethal than cosmic rays for organic
compounds in interplanetary space.
The Tanpopo Mission is the first Japanese astrobiology
space experiment, which is now scheduled to start in 20143).
Samples will be retrieved 1-3 years after launch. We can
expect to have the first IDPs sampled in space to see what
kind of organics can be delivered by IDPs. In addition to this
capture experiments, we are going to expose selected organic
compounds and meteorite powders to space environments to
examine stability and alteration of possible extraterrestrial
organic compounds in space. In this paper, we described
objectives of the organics-exposure experiments in the
Tanpopo Mission, and showed preliminary results of ground
simulation experiments for the preparation of the mission,
together with experimental setups in space.

precursors) and nucleic acid bases were irradiated with


continuous emission (soft X-rays to IR; hereafter referred to as
soft X-rays irradiation) from BL-6 of NewSUBARU
synchrotron radiation facility (Univ. Hyogo). They were also
irradiated with heavy ions (eg., 290 MeV/u C6+) from HIMAC
accelerator (NIRS, Japan).
After soft X-rays irradiation, water insoluble materials were
formed. After irradiation with soft X-rays or heavy ions,
amino acid precursors (CAW and hydantoins) gave higher
ratio of amino acids were recovered after hydrolysis than free
amino acids. Nucleic acid bases showed higher stability than
free amino acids.
Complex amino acid precursors with high molecular
weights could be formed in simulated dense cloud
environments. They would have been altered in the early
solar system by irradiation with soft X-rays from the young
Sun, which caused increase of hydrophobicity of the organics
of interstellar origin. They were taken up by parent bodies of
meteorites or comets, and could have been delivered to the
Earth by meteorites, comets and cosmic dusts. Cosmic dusts
were so small that they were directly exposed to the solar
radiation, which might be critical for the survivability of
organics in them. The stability of IDPs organic compounds in
space environments will be tested in the exposure experiments
in the Tanpopo Mission.

2.

3.1. Selection of target molecules


It has been shown that amino acid precursors can be formed
in interstellar environments5-8), and that amino acids or their
precursors are present in carbonaceous chondrites9,10). It was
also reported that glycine was found in cometary dusts
returned by the Stardust Mission11). Thus it is possible that
IDPs that has been ejected from asteroids or comets have
amino acids or their precursors. Among a great number of
amino acids found in carbonaceous chondrites, we selected
glycine and isovaline to study the stability of amino acids in
space. The former is one of the simplest and the most
abundant protein amino acids. The latter is non-protein
amino acids and enantiomeric excesses were reported in
isovaline extracted from carbonaceous chondrites 12). Their
possible precursors, hydantoin and 5-ethyl-e-methyl hydantoin
were also added to the target list, together with complex
amino acid precursors, CAW.

3.
Ground Simulation of Alteration
Acid-Related Compounds in Earth Orbit

Origins of Organic Compounds in IDPs

It was suggested that organics in extraterrestrial bodies such


as meteorites, comets and IDPs were originally formed in ice
mantles of interstellar dusts in dense cloud, since isotopic
studies of organic compounds in meteorites and comets
suggested that they were formed in quite cold environments4).
Irradiation of frozen mixture of possible interstellar molecules
including CO (and/or CH3OH), NH3 and H2O with
high-energy particles5,6) or ultraviolet light7,8) gave amino acid
precursors (molecules that give amino acids after hydrolysis)
with high molecular weights [1]. Such complex organic
molecules were taken in planetesimals or comets in the early
solar system. In prior to the generation of the terrestrial life,
extraterrestrial organics were delivered to the primitive Earth
by such small bodies as meteorites, comets and space dusts.
These organics would have been altered by cosmic rays and
solar radiation (UV, X-rays) before the delivery to the Earth.
We examined possible alteration of amino acids, their
precursors and nucleic acid bases in interplanetary space by
irradiation with high-energy photons and heavy ions.
A mixture of CO, NH3 and H2O was irradiated with
high-energy protons from a van de Graaff accelerator (TIT,
Japan). The resulting products (hereafter referred to as
CAW) are complex precursors of amino acids. CAW, amino
acids (DL-isovaline, glycine), hydantoins (amino acid

of

Amino

3.2. Irradiation of target molecules with UV, -rays and


Heavy Ions
In the space environments, UV-light and cosmic rays
(high-energy ions and -ray) will cause the alteration of
organic compounds. Therefore, experiments to examine
possible photolysis and radiolysis of organic compounds in
space environments were performed.
In order to examine the stability of the target molecules
against VUV, Xe-excimer lamp (at 172 nm; Ushio standard

Table 1.

Estimated recoveries after 1 year irradiation in Earth Orbit


UV irradiation

Cosmic rays
60

172 nm
2 10

-5

Isovaline

3 10

-5

Glycine

Co -ray

Heat

Total

Carbon ion

100 C

1.0

1.0

1.0

2 10-5

> 0.99

> 0.99

1.0

3 10-5

Hydantoin

0.29

1.0

1.0

1.0

0.29

Ethylmethylhydanotin

0.72

> 0.99

> 0.99

>0.99

0.72

Complex organics (CAW)

N.A.

1.0

1.0

1.0

N. A.

N.A.: not available

type excimer light emission unit) was used. Solution of


exposure samples were added into the small hole (1 mm) on
a SUS plate and dried under reduced pressure. Then the plate
was placed in the vacuum chamber and were irradiated for 6.2
h at 4 1014 photons s-1 cm-2 and the irradiation was
equivalent for 4 days irradiation around the ISS orbital. After
irradiation, samples were extracted with water and analyzed
by HPLC.
We also irradiated the target molecules with synchrotron
radiation soft X-rays at NewSUBARU BL06 (University of
Hyogo, Japan), with -rays from a 60Co source (Quantum
Beam, JAEA, Japan) and with carbon ion beam (290 MeV/u)
at the HIMAC biology beam line (NIRS, Japan). In each
irradiation experiment, amino acids or their precursors were
irradiated in a solid state. Thermal stability at 100C of the
compounds were also tested.

can expect that appreciable percentage of amino acid


precursors would survive after 1 years exposure in LEO,
while very limited part of the original free amino acids would
be recovered.
4. Exposure of meteorite grains for understanding of
space weathering effect on asteroidal regolith
Space weathering on the surface regolith of asteroids
could have been one of the important processes for chemical
evolution in the early Solar System. However, it has been
difficult to identify the records from meteorite samples that
are lack of asteroid geologic information. For the first time,
the preliminary examination of Itokawa asteroid particles
returned by Hayabusa mission has revealed the evidence of
space weathering on the mineral particles14) and the irradiation
history of the asteroid regolith15). The space weathering effect
on organic compounds has been unknown since organic
compounds have not been detected from Itokawa particles16),
but we will consider more seriously having information about
the processes in the world future asteroid sample return
missions, such as Hayabusa-2, OSIRIS-REx, and Marco
Polo-R, which will go sampling the surface regolith of
carbonaceous asteroids.
Kanuchova et al.17) have shown the changes induced by
energetic ion irradiation in the ultraviolet-visual-near-infrared
(UV-Vis-NIR) reflectance spectra of olivine pellets covered
by polystyrene. However, polystyrene has quite different
compositions to those of organic materials in asteroids
(meteorites), and thus it will be necessary to examine more
realistic samples. In Tanpopo project, we propose to conduct
an exposure experiment of meteorite grains on ISS in order to
understand the space weathering alteration of molecular,
isotopic, and morphological compositions of organic materials.
The Low Earth Orbit environment satisfies the similar
conditions to those on the surface regolith of asteroids, e.g.,
multiple irradiation energies (e.g., UV, radiation) and
temperature cycle in sunrise and sunset, which are difficult to
reproduce in a laboratory experiment. For a sample
preparation, suspended Murchison meteorite particles in water
will be dropped and fixed onto a silicon nitride membrane
window TEM grid and the grid will be placed on the exposure
plate. After 1-3 years of exposure at ISS, the returned samples

3.3. Stability of Amino Acids and Their Precursors


against High-Energy Photons and Particles
-Rays and heavy ion beam irradiation with dose of ISS
environment for one year induced little decomposition of
organic compounds. However, UV irradiation was critical for
organic compounds. Although almost all glycine and isovaline
were
decomposed,
recovery
of
hydantoin
and
5-ehtyl-5-methyl hydantoin were approximately 29 % and
72%, respectively, with UV dose of ISS environment for one
year. Furthermore, CAW was more stable than hydantoins.
Amino acids precursors, especially, complex organics were
more stable than free amino acids in space environments.
Soft X-rays irradiation experiments showed the same
tendency:
Free amino acids (glycine and isovaline)
decomposed more rapidly than their precursors (hydantoins
and CAW).
Table 1 shows estimated recovery ratios after 1 years
exposure to space environments in the exposed facility of the
international space station (EF/ISS). Here the flux of VUV
on ISS orbit was estimated to be 0.12 J m-2 s-1 for 120 nm to
200 nm radiation13). Thus, the yearly dose of VUV172 nm in
LEO was estimated to 3.8 103 kJ m-2.
It can be seen that the most fatal factor for organic
compounds in low Earth orbit (LEO) is UV, and effects of the
other factors (cosmic rays and heat) would be negligible. We
3

Figure 3. Absorption spectra of alanine film. An arrowshows the


cut-off wavelength of SiO2.
Figure 1. An apparatus for space exposure experiments of microbes
and organic compounds in Tanpopo mission. This is a rectangular
solid of 100 mm 100 mm 20 mm. It can divide into 20
independent small chamber and we can independently use each
chamber (Figure 2).

Figure 4. 172 nm photolysis curve of alanine film. Lamp


intensity I0 was 5.2 x 1015 photons s-1.

O/OREOS mission which investigates


photocatalytic role of mineral surface20).
5.

Figure 2. The cross section of a unit cell. An MgF2 (or quartz)


window with 16mm in diameter is attached at the top of the unit, and

the

effects

of

Exposure Facility for the Tanpopo Mission

An apparatus for exposure experiments is shown in Fig. 1.


This is a rectangular solid of 100 mm 100 mm 20 mm. It
can divide into 20 independent small chamber and we can
independently use each chamber. The cross section of a
small chamber is shown in Fig. 2. An MgF2 window of
16mm in diameter is attached at the top of the small chamber,
and a filter of 0.3 mm is at the bottom. We can expose some
samples, including organic compounds and microorganisms,
without contamination of surroundings.

0.3 m filter is at the bottom to contain the microbe while the sample
is exposed to the space vacuum.

will be analyzed by micro-X-ray absorption near edge


structure (XANES), transmission electron microscope (TEM),
and nano-secondary ion mass spectrometry (SIMS). The
obtained molecular and isotopic compositions will be
compared with those of pre-exposed meteorite samples.
De Gregorio et al.18) has demonstrated the increase of the
isotopic ratio of deuterium to hydrogen (D/H) of polymer
resins after the electron irradiation. Dworkin et al.19) has
synthesized organic vesicular structures by UV photolysis of
interstellar ice analogs with a repetitive warming-freezing
process. According to these experiments, the alteration of
chemical and/or morphologic compositions of meteoritic
organics will be expected after the experimental space
weathering. Finally, it will be expected to learn the role of
minerals for the alteration of organics in meteorite matrix,
which is a complementary study with SEVO experiment in

6. Vacuum Ultraviolet Dosimetry and Photochemistry of


Alanine Film
In order to develop the vacuum ultraviolet dosimeter, it is
necessary to find material of which main absorption band is at
vacuum ultraviolet VUV region. Here we will try an alanine
film deposited on a quartz or MgF2 windows. Because
absorption cross-section is negligible small at the wavelength
region longer than 200 nm as shown in Fig. 3, this alanine
dosimeter is sensitive at the region of 160 < < 190 nm when

3 amino acid precursors (hydantoin, 5-ethyl-5-methyl


hydantoin, and complex amino acid precursors CAW
synthesized from CO, NH3 and H2O by proton irradiation.
They were exposed to solar VUV and cosmic radiation on
JEM-EF for 1-3 years. Powder of the Murchison meteorite
will also be exposed. Dose will be monitored with the
alanine VUV dosimeter.
After the laboratory simulation experiments, we estimate
that at least amino acid precursors will be survived after a few
years expose in space. Detailed analysis of the exposed
samples after return to the Earth, we will be able to discuss on
the roles of extraterrestrial organics in chemical evolution and
generation of life on the Earth or elsewhere.
Acknowledgments
a SiO2 window is chosen.
According to the photolysis experiment with 172 nm
excimer lamp by Izumi et al.21), alanine film was decomposed
as shown in Fig. 4 with the rate constant of k =1.8 10-18
photon-1; dn/dt = -knI0, where n the number of survived
alanine molecules and I0 the number of absorbed photons per
unit time. Using these data, we will develop a VUV dosimeter
as shown in Fig. 5.
In the figure, the mesh was used to
guard and the coating material is used to prevent the
sublimation loss of alanine molecule from the film.
Survival rate of the alanine film after irradiation at the
location of the international space station was roughly
estimated from the solar irradiance spectrum observed by
satellite13) and from an appropriate attenuation factor 0.015 by
the mesh and a neutral density filter, to be 70, 49 and 34 %
after one, two and three years, respectively.
Photochemical reaction will be studied through the analysis
of returned samples. One of important target molecule is
alanylalanine. According to Izumi et al. 21), quantum yield of
alanylalanine production was roughly estimated to be 1.3
10-3 photon-1 at the beginning stage of irradiation. Detection of
alanylalanine is the direct evidence of chemical evolution
resulted from solar irradiation at the space.

The present author thank to Dr. Katsunori Kawasaki, Dr.


Yoshiyuki Oguri, Dr. Hitoshi Fukuda (Tokyo Institute of
Technology), Dr. Issay Narumi (Toyo University) for their
kind help in irradiation experiments. They also thank to Mr.
Takeo Kaneko and Dr. Yumiko Obayashi for their
collaboration in analysis.
The present work was partly supported by JSPS KAKENHI
(Grant No. 24654181) and by JAXA Space Utilization WG
program.
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7.

Conclusions
The Tanpopo Mission is the first astrobiological mission by
utilizing ISS/JEM. Among a number of subthemes of the
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IDPs could deliver organic compounds more safely than large
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