Astrochemistry
The Cradle of Life
i Professor Nigel Mason
The Open University
a
Introduction
Perhaps the great unanswered questions of
modern science is
Where and how did life begin on Earth ?
And
Is there life elsewhere in the universe ?
Introduction
Lets take a vote !
Who believes there is life elsewhere in
the universe ?
Introduction
Lets ask a slightly different question
Who believes there is intelligent life
elsewhere in the universe which is able to
establish a science programme to look for life ?
Introduction
To answer the questions
Where and how did life begin on Earth ?
And
Is there life elsewhere in the universe ?
We need to answer scientific questions
Are the conditions for sustaining life common
throughout the universe ?
Introduction
To answer the questions
Where and how did life begin on Earth ?
And
Is there life elsewhere in the universe ?
We need to answer scientific questions
Are the conditions for sustaining life common
throughout the universe ?
How is the material needed for life (pre-biotic
material) formed ?
Chemical origins of life
To understand how life was formed we need
to know how and where chemical elements
of life were made
What are major chemical elements of life ?
Chemical origins of life
The major molecule of
life (as we know it) is
DNA
Deoxyribonucleic acid
Major elements are
Carbon, hydrogen, oxygen,
nitrogen and phosphorous.
Nucleobases
Adenine
Guanine
Thymine
Cytosine
Paired in DNA
AT
CG
Building DNA
DNA is made up of smaller molecules which must
have assembled first from smaller molecules such
as Amino acids
So if we want to know how DNA was formed we
start by looking for how these smaller (prebiotic)
molecules are formed
History of Origins of Life Research
Scientific investigation of origins of life are recent
Aleksandr Oparin 1894 -1980
Oparin considered how basic organic chemicals
might form into larger chemical systems which were
the possible precursors of cells - from which
primitive living things could develop.
He suggested life may have begun in early oceans
Since the surface was too exposed to UV light,
volcanic eruptions acid rain and meteor impacts for
life to survive,
Exploring origins of life
Oparin’s hypotheses were not tested for some 40 years until Harold
Urey and Stanley Miller March 7, 1930 - May 20, 2007 performed
a famous experiment to see if the chemical ingredients of life can be
made in the atmosphere of a planet .
The UREY MILLER Experiment.
The Urey Miller
Experiment
Mixture of Water,
Hydrogen, Methane and
Ammonia
Generate a discharge as
in lightening
See what you make !
Molecules formed in planetary
atmospheres – Urey Miller expts
CH4 + NH3 + H2
+ energy
?
e.g. in the gaseous
atmosphere’s of
new planets
Glycine
Amino acid
The OU Urey Miller experiment
Similar in design to the
original.
2 L glass bulb for the
“atmosphere”
200 ml water bulb
Heating provided by
heating tapes
Urey Miller Results
• Urey-Miller was run for a O O
week, liquid was H3C
OH H2N C
extracted from the flask NH2
CH2 OH
• Analysed with paper
chromatogram Alanine (Ala) Glycine (Gly)
• 3 Amino acids identified,
Glycine, α-alanine and β-
alanine
• Hence it is possible to
form prebiotic molecules
from basic chemistry
But we now know …
These were not the gases in early earth
atmosphere (more CO2 and SO2)
It takes too long to build these molecules –
Indeed according to our models we are not here
yet !!!
But what if the ‘building blocks’ are
formed in space itself ?
Are biomolecules transported to
Earth on comets, meteorites ?
Are biomolecules made in transit through
Earth’s atmosphere on comets etc ?
Meteorites give evidence that amino acids are
present in large numbers – some of which are
not found naturally in terrestrial life
So are prebiotic molecules of life made in
space ?
The Interstellar Medium is rich in molecules…
from the simplest molecule (H2)
to those necessary for the formation of life
Credit: R.Ruiterkamp
>140 Interstellar and Circumstellar Molecules
2 3 4 5 6 7 8 9 10 11
H2 C3 c-C3H C5 C5H C6H CH3C3N CH3C4H CH3C5N? HC9N
AlF C2H l-C3H C4H l-H2C4 CH2CHCN HCOOCH3 CH3CH2CN (CH3)2CO
AlCl C2O C3 N C4Si C2H4 CH3C2H CH3COOH (CH3)2O NH2CH2COOH ? 12
C2 C2S C3O l-C3H2 CH3CN HC5N C7H CH3CH2OH C6H6
CH CH2 C3S c-C3H2 CH3NC NH2CH3 H2C6 HC7N
CH+ HCN C2H2 CH2CN CH3OH HCOCH3 CH2OHCHO C8H 13+
CN HCO CH2D+ ? CH4 CH3SH c-C2H4O HC11N
CO HCO+ HCCN HC3N HC3NH+ CH2CHOH PAHs
Glycine ?
CO+ HCS+ HCNH+ HC2NC HC2CHO C60+
CP HOC+ HNCO HCOOH NH2CHO
CSi H2O HNCS H2CHN C5 N Acetic Acid
HCl H2S HOCO+ H2C2O
KCl HNC H2CO H2NCN
NH HNO H2CN HNC3
NO MgCN H2CS SiH4
NS MgNC H3O+ H2COH+ Benzene
NaCl N2H+ NH3
OH N2O SiC3 Glycolaldehyde
PN NaCN
SO OCS Cyanopolyynes
SO+ SO2 Formic Acid
SiN c-SiC2
SiO CO2
SiS NH2
CS H3+
HF SiCN
SH
AlNC
FeO National Radio Astronomy Observatory
http://www.cv.nrao.edu/~awootten/allmols.html
What chemistry can occur in such
environments ?
• Temperatures are low … (As low as 10K)
• In the ISM the density is extremely low … so probability of
collisions is low
• Hence it appears impossible to support chemistry !
But evidence of molecular species shows there must be
complex chemistry !
What chemistry can occur in such
environments ?
• At low temperatures there is little or no thermal/kinetic
energy
• So chemistry must occur through reactions that need no
energy.
• Or
• Reactions that are assisted e.g. by light
What chemistry can occur in such
environments ?
Ion-Molecule reactions are a typical example of a reaction
that do not require energy input
e.g. NH3+ + H2 → NH4+ + H
Ar+ + H2 → ArH+ + H
He+ + H2 → He + H+ + H
H2- + H → H + H2 + e-
What chemistry can occur in such
environments ?
However neutral – neutral reactions can also occur at low
temperatures.
H2O + Cl → HCl + O
F + D2 → DF + D
Indeed the reaction rate may INCREASE as the temperature falls
What chemistry can occur in
such environments ?
Supersonic crossed beam machine for radical-radical studies.
CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme)
to study neutral-neutral reactions and energy transfer processes in the
gas phase down to temperatures as low as ~10 K. (Rennes)
What chemistry can occur in such
environments ?
But such gas phase experiments can not explain all the
chemistry in the ISM
E.g. the formation of H2 …. the most common molecule in the ISM can
not be formed in the gas phase
Instead it is formed by reactions on the surface of
little dust grains made when stars die !
Little pieces of Carbon – like the soot on your
Macdonalds ‘flame grilled’ burger
Or silicon ( sand !!)
Chemistry on Dust grains
• Some of these grains
are covered with an icy •The ices in the
mantle formed by
freezing out of
mantle are
atoms/molecules from bombarded with
the gas phase cosmic rays, Ions,
solar UV, electrons.
• Hence we need to •Chemistry occurs
explore ice
chemistry ! making molecules.
Cryogen inlet via
• Vacuum chamber to mimic transfer line
empty space:
– P~10-8 - 10-10 mbar 25.2
• Still > a million times higher
Temperature
than ISM! controller
• Temperature very cold in space
Continuous
– Continuous flow LHe/LN2 flow cryostat
Ion gauge
cryostat
• 12 K < T < 450 K To
pumping
• Material to mimic grains station
• Make ice Samples Resistive heater
• Use spectroscopy to see Copper sample
mount MgF2/ZnSe
what you make Thermocouples substrate
Sources Detectors
- UV-VIS / FTIR - UV-VIS / FTIR detector
spectrometer - Photomultiplier Tube
- Synchrotron
Sources
E-gun
Synchrotron
Ion Source
Experimental studies of chemical processing
of astrochemical ices
First we need to find a
mimic of star light !
Stars are fuelled by
nuclear reactions
We can’t use these in a
laboratory
Experiments at Synchrotron
Facilities
Mimicing star light
UK Daresbury Aarhus Denmark
Irradiation of H2O:CO2 ice
Before irradiation
CO2
CO2
13CO
2
H2O
H2O:CO2
H2O
H2O
Irradiation of H2O:CO2 ice
After irradiation for 1 hour
CO2
CO2
13CO
2
H2O
H2CO3 H2CO3
(1703) (1488)
H2CO3
CO (1295)
H2CO3 (2140)
CO3
H2O:CO2 (2850) H2CO3 (2044)
(2580)
H2O
H2O
T(K)
250 Warm-up CO2
+Irradiation of H2O
H2O:CO2 ice
H2O
200
CO2
H2O
150 H2O
CO
100
H2O
50
T(K)
250 Warm-up after H+ CO2
Irradiation of H2O
H2O:CO2 ice
H2O
200
CO2
H2O
150 H2O
CO
100
H2O
50
T(K)
250 Warm-up after H+ CO2
Irradiation of H2O
H2O:CO2 ice
H2O
200
CO2
H2O
150 H2O
CO
100
H2O
50
T(K)
250 Warm-up after H+ CO2
Irradiation of H2O
H2O:CO2 ice
H2O
200
CO2
H2O
150 H2O
CO
100
H2O
50
T(K)
250 Warm-up after H+ CO2
Irradiation of H2O
H2O:CO2 ice
H2O
200
CO2
H2O
150 H2O
CO
100
H2O
50
T(K)
250 Warm-up after H+ Crystalline
Irradiation of H2O
CO2
H2O:CO2 ice
H2O
200
CO2
H2O
150 H2O
CO
100
H2O
50
T(K)
250 Warm-up after H+
Irradiation of
H2O:CO2 ice
200
150 H2O
CO2
100
H2O H2O
50
T(K)
250 Warm-up after H+
Irradiation of
H2O:CO2 ice
200
150
100 H2O
CO2
50
T(K)
250 Warm-up after H+
Irradiation of
H2O:CO2 ice
200
150
H2CO3
H2CO3
100
50
Conclusions ?
Experiments show possible to form molecules
under conditions prevailing in the ISM
But these are small molecules
But can make larger (biological molecules) ?
So can we go on to make building
blocks of life ?
How to create an amino acid ?
How to create a sugar in space ?
Synthesis in the ice mantles ?
Electron Induced Chemistry
• Some examples of laboratory study of electron induced synthesis of
molecules under astrochemical conditions.
• Chemical synthesis in 1:1 Mixture of NH3:CO2 Ice with 1 keV
electrons at 30 K
05th Jan 2006 Chemistry of Planets
OCN, CO production
05th Jan 2006 Chemistry of Planets
Formation of ammonium carbamate
05th Jan 2006 Chemistry of Planets
Electron Induced Chemistry
• Some examples of laboratory study of electron induced synthesis of
molecules under astrochemical conditions.
• Chemical synthesis in the Irradiation of 1:1 Mixture of
NH3:CH3OH ice with 1 keV electrons at 20 K
05th Jan 2006 Chemistry of Planets
Formation of ethylene glycol in pure methanol ice
HOH2C-CH2OH
05th Jan 2006 Chemistry of Planets
Formation of methyl formate
CH3OHCO
05th Jan 2006 Chemistry of Planets
Formation of formamide HCONH2
(Khanna, Lowenthal et al. 2002)
05th Jan 2006 Chemistry of Planets
Irradiation of methylammine and carbon dioxide ice makes
glycine simple amino acid
And So ?
In the lab we can now simulate what happens in
space
We can show that the basic molecules of life can
be made ‘easily’ throughout the universe by
uniform process.
So the chemistry for life exists ‘everywhere’
But what does this tell us about the origins of life
on earth/elsewhere ??
We have the ‘building blocks’ but
how do they assemble ?
How do/did simple molecules assemble to make
DNA ?
We have the ‘building blocks’ but
how do they assemble ?
How do/did simple molecules assemble to make
DNA ?
WE DONT KNOW !!!!!!!
Science does not have all the answers !
There is still much to do
There are known knowns
Known unknowns
and
Unknown unknowns
Known unknowns !
The spontaneous formation of complex
polymers from simple monomers is not simple
and
The physical/chemical conditions that allow the
simple molecules to form (eg glycine) are the
same that destroy larger molecules (DNA )
So where do/did large molecules assemble ?
In a prebiotic soup
Like the early oceans
REMEMBER
OPARIN
Where they were
shielded from harsh
surface conditions
Smokers on seafloor
Other places where such assembly could begin
Clay world: Chemical reactions taking place
within clay substrates or on the surface of rocks
whch act as a ‘template’ for molecular assembly.
Other places where such assembly could begin
In ‘ponds’: Chemical
reactions taking place
within pools around
volcanic vents and
geysers
One possible clue
Homochirality
Life is chiral !!
One possible clue
Amino acids are left handed
Nucleic acid sugars right handed.
Homochirality is essential for the formation of
functional proteins.
How does/did homochirality arise ???
We don’t know but it might give us a clue as
ot way molecules are assembled
So back to opening question
Is there life on another planet ??
The scientific search for Life
Not aliens !
More likely bacterial, photosynthetic
Cyanobacteria
Architects of earth's atmosphere
Life on Mars ?
More and more evidence suggests the
Martian Surface was once capable
of sustaining flowing water
ExoMars!
Life on Mars ?
Methane emissions
Fossil evidence
Martian Meteorites
Only 34 have been identified most since 2000
Meteorite ALH 84001 in 1996 announce
possible signs of fossil life
Martian Meteorites
Now not believed to be fossils of bacteria
Search for Exoplanets
http://en.wikipedia.org/wiki/List_of_extrasolar_planets
http://en.wikipedia.org/wiki/Extrasolar_planet
We have already found >500 extra-solar Planets
Number of extrasolar planet discoveries per year as of 3
October 2010, with colours indicating method of detection
Looking for planets
Methods
Radial velocity
/Doppler method
Transit method
Microlensing
Astrometry
Direct image of exoplanets around the star HR8799 using Hale telescope
Looking for planets
Radial velocity/Doppler method
This has been by far the most productive technique used by
planet hunters. It is also known as Doppler spectroscopy.
The method is distance independent, but requires high
signal-to-noise ratios to achieve high precision, and so is
generally only used for relatively nearby stars out to about
160 light-years from Earth.
It easily finds massive planets that are close to stars, but The High Accuracy Radial
detection of those orbiting at great distances requires many velocity Planet Searcher
(HARPS) is a high-precision
years of observation. Planets with orbits highly inclined to echelle spectrograph
the line of sight from Earth produce smaller wobbles, and installed in 2002 on ESO's
are thus more difficult to detect. 3.6m telescope at La Silla
One of the main disadvantages of the radial-velocity Observatory in Chile
method is that it can only estimate a planet's minimum
16 exoplanets
mass . found
Looking for planets
UK University programme to
look for planets using standard
cameras
The Transit method
The future imaging the planet
A possible design for
Darwin, a proposed
ESA telescope to explore
extrasolar planets
But what are biomarkers of life ?
CO2/methane/water needed for life ?
But have both biotic and abiotic sources
but ozone was believed to be the BEST
BIOMARKER
Ozone is signature on Earth of molecular oxygen rich
atmosphere
Prominance since 1980 due to problems of Ozone Depletion
Ozone formation
Ozone is formed in a three body reaction since
without a third body to stabilise the product
ozone it would rapidly redissociate
O + O2 + M → O3 + M
Ozone Destruction
OH radicals destroy ozone in a catalytic cycle;
OH + O3 --> HO2 + O2
HO2 + O3 --> OH + 2O2
Ozone Depletion Studies in the
Ultra-Violet
Ozone in the terrestrial
atmosphere absorbs the
solar UV preventing it
from reaching the Earth’s
surface.
Destruction of the ozone
in the Earth’s atmosphere
leads to increased UV flux
at the surface. www.iof.fraunhofer.de/.../
_media/uv_bd_e.gif
Ozone Depletion Studies in the Ultra-Violet
UV leads to genetic (DNA) damage
(erythema/sunburn)
bse.unl.edu/.../images_ undergrad/sunburn.JPG
So can ozone be formed on other
planets ?
Yes is found on Mars
So could there ever have been a significant
ozone layer on Mars ?
There are small quantities of ozone in Martian
atmosphere
SPICAM data from Mars Express
So can ozone be formed on other
planets ?
Recently found on
Ganymeade- moon of Jupiter
Dione and Rhea moons of Saturn
Ices in the Solar System
Mercury Europa Ganymede Callisto Io
Earth
Mars
Saturn Dione Enceladus Rhea Tethys Mimas
Miranda
Ariel: CO2 Umbriel Oberon Pluto & Charon
Neptune Triton
Ices in the Outer Solar System
Planet Satellite Ices Ehrenfreund and Fraser (2003)
Jupiter Io SO2, SO3, H2S?, H2O?
Europa H2O, SO2, SH, CO2, CH, XCN, H2O2, H2SO4
Ganymede H2O, SO2, SH, CO2, CH, XCN, O2, O3
Callisto H2O, SO2, SH, CO2, CH, XCN
Saturn Mimas H2O
Enceladus H2O
Tethys H2O
Dione H2O, C, HC, O3
Rhea H2O, HC?, O3
Hyperion H2O
Iapetus H2O, C, HC, H2S?
Phoebe H2O
Rings H2O
Uranus Miranda H2O, NH3
Ariel H2O, OH?
Umbriel H2O
Titania H2O, C, HC, OH?
Oberon H2O, C, HC, OH?
Neptune Triton N2, CH4, CO, CO2, H2O
Pluto Charon H2O, NH3, NH3 hydrate
N2, CH4, CO
KBOs H2O, HC-ices (CH4, CH3OH), HC, silicates
But …
Ozone on such moons is not formed in the
‘lunar’ atmosphere but rather by ion
bombardment of the icy surfaces
So ozone is not a unique biosignature and does
not indicate oxygen atmosphere or
photosynthesis
But what to look for ?
So how about looking for a real biomarker
Eg chlorophyll a pigment in plants ?
Remote Sensing
Identifying life on Earth from Space
Monoterpenes
The citrus smell
Eucalyptus smell
Can we adopt techniques from
environmental research ?
Measure the reflectance spectra
Typical Reflectance
Spectrum of Vegetation.
Common wavelength bands
used in optical remote
sensing of vegetation:
A: blue band, B: green band;
C: red band;
D: near IR band; E: short-
wave IR band
The absorbance spectrum of coarsely separated
chlorophyll from common box leaves.
-1
And how do we find out more of
early life on earth ??
Need more field studies to look for fossils
And to develop more computer models of the
developing early terrestrial atmosphere (using
ideas of sophisticated climate programmes).
And how do we find out more of
early life on earth ??
Stromatolites -- are these what we look for ?
So there is much to be done
and there is a new name for this research field
ASTROBIOLOGY
Astrobiology has come of age
And it is an exciting (the
most exciting ?) area of
scientific research….
Bringing together The
researchers in a truly
interdisciplinary programme
INTERNATIONALLY !
And it is an exciting (the most exciting ?) area of
scientific research….
Bringing together researchers in a truly
interdisciplinary programme !
INTERNATIONALLY !!!
ASTROBIOLOGY
A field combining astronomy, biology, Chemistry and
physics
This century we may answer the questions
Is there life on other planets in other solar systems
And
we may understand the chemistry of how life begins
