New Science from new New Science from new Technology:Technology:

NanoSIMS and RIMS NanoSIMS and RIMS

Peter HoppePeter Hoppe

Max-Planck-Institute for ChemistryMax-Planck-Institute for Chemistry

IAU Meeting 2006IAU Meeting 2006

PraguePrague

August 21, 2006August 21, 2006

OutlineOutline1. 1. IntroductionIntroduction2.2. NanoSIMS 50 Ion MicroprobeNanoSIMS 50 Ion Microprobe3.3. RIMS - CharismaRIMS - Charisma4.4. NanoSIMS StudiesNanoSIMS Studies

4.1. Submicrometer-sized Presolar Grains4.1. Submicrometer-sized Presolar Grains4.2. Isotopic Homogeneity within Presolar 4.2. Isotopic Homogeneity within Presolar GrainsGrains4.3. Presolar Silicates4.3. Presolar Silicates4.4. Coordinated NanoSIMS-TEM Studies4.4. Coordinated NanoSIMS-TEM Studies

5.5. RIMS StudiesRIMS Studies5.1. SiC Mainstream Grains5.1. SiC Mainstream Grains5.2. SiC X Grains5.2. SiC X Grains

6.6. SummarySummary

Introduction (I)Introduction (I)

A b u n d a n c e ( p p m )

S i C

D i a m o n d

C o r u n d u m

S i 3 N 4

1 0 - 3 1 0 - 2 1 0 - 1 1 0 0 1 0 1 0 2 1 0 3 1 0 4

S p i n e l

S i l i c a t e s i n M e t e o r i t e s

S i l i c a t e s i n I D P s

G r a p h i t e

Presolar MineralsPresolar Minerals

Introduction (II)Introduction (II)

1 0

1 0 2

1 0 3

1 0 4

1 0 5

1 0 0Novae

1 0 0 1 0 41 0 1 0 2 1 0 31 0 - 1 1 0 5

MainstreamType A&BType XType Y&Z

12C/13C

14N

/15N

C-rich zonein SN II

CNO cycle

C stars

Presolar SiC PopulationsPresolar SiC Populations

Introduction (III)Introduction (III)

Noble gas mass spectrometry of bulk Noble gas mass spectrometry of bulk samples (late 1980s, early 1990s)samples (late 1980s, early 1990s)

Conventional SIMS (late 1980s, Conventional SIMS (late 1980s, 1990s, early 2000s)1990s, early 2000s)

RIMS (late 1990s)RIMS (late 1990s) NanoSIMS (2000s)NanoSIMS (2000s)

Isotope Analyses of Presolar GrainsIsotope Analyses of Presolar Grains

Introduction (IV)Introduction (IV)

NanoSIMS:NanoSIMS: Analysis of submicrometer-sized presolar dustAnalysis of submicrometer-sized presolar dust In-situ search for presolar dustIn-situ search for presolar dust Investigation of isotopic heterogeneity within Investigation of isotopic heterogeneity within

grainsgrains

RIMS:RIMS: Isotopic compositions of heavy elements in Isotopic compositions of heavy elements in

individual grainsindividual grains

The Role of NanoSIMS and RIMSThe Role of NanoSIMS and RIMS

NanoSIMS 50 (I)NanoSIMS 50 (I) Commercial ion microprobe from CamecaCommercial ion microprobe from Cameca Introduction to field of cosmochemistry in 2001 Introduction to field of cosmochemistry in 2001

(Washington University, St. Louis and MPI for (Washington University, St. Louis and MPI for Chemistry, Mainz)Chemistry, Mainz)

Three fundamental features:Three fundamental features:1. Small beam size (down to 50 nm for Cs1. Small beam size (down to 50 nm for Cs++--ions)ions)2. High transmission at high mass resolution2. High transmission at high mass resolution (30x higher than in the IMS3f for conditions (30x higher than in the IMS3f for conditions used for O-isotopic measurements) used for O-isotopic measurements)3. Simultaneous detection of up to five isotopes3. Simultaneous detection of up to five isotopes (minimum mass separation is M/30, i.e., (minimum mass separation is M/30, i.e., isotopes up to mass 30 (Si) can be measured isotopes up to mass 30 (Si) can be measured simultaneously simultaneously

NanoSIMS 50 (II)NanoSIMS 50 (II)

RIMS - CharismaRIMS - Charisma Most advanced (in the field): CHARISMAMost advanced (in the field): CHARISMA

(Chicago-Argonne Resonant Ionization(Chicago-Argonne Resonant IonizationSpectrometer for Mass Analysis)Spectrometer for Mass Analysis)

Laser ablation + laser ionization + TOF-MSLaser ablation + laser ionization + TOF-MS Superior to SIMS for trace elements , Superior to SIMS for trace elements ,

especially such with small ion yields in SIMS especially such with small ion yields in SIMS Basically a single-element-methodBasically a single-element-method First applications: Fe, Sr, Zr, Mo, Ru, and Ba First applications: Fe, Sr, Zr, Mo, Ru, and Ba

in single presolar SiC & graphite grainsin single presolar SiC & graphite grains Prospects:Prospects:

““Useful yield” of current setup ~ 1 %Useful yield” of current setup ~ 1 % Planned modification: aiming at ~ 30%Planned modification: aiming at ~ 30%

CHARISMA – Schematics (I)CHARISMA – Schematics (I)

atoms & molecules

ions

Mo Ba

Ti2

Ti

Si

Ti+ Si+

Neutral species drift up; ions are

suppressed

Gold mount

Mo

Ba+

Ti2

Ti

Si

Ba ions are accel- erated and mass- analyzed with a

time-of-flight mass spectrometer

Mo Ba+

Ti2

Ti

Si

Two lasers tuned to resonantly ionize

Ba are fired just above surface

Ablationlaser fires

SiC grainfocus to 1 µm

CHARISMA – Schematics (II)CHARISMA – Schematics (II)

Most presolar grains are submicrometer Most presolar grains are submicrometer in sizein size Previous characterization was biasedPrevious characterization was biased

NanoSIMS made it possible to obtain NanoSIMS made it possible to obtain information on previously largely information on previously largely unexplored presolar grain types:unexplored presolar grain types: Sub-population of presolar SiC with specific Sub-population of presolar SiC with specific

Si-isotopic signatureSi-isotopic signature Presolar spinel (MgAlPresolar spinel (MgAl22OO44))

NanoSIMS Studies (I)NanoSIMS Studies (I)Submicrometer-sized Presolar GrainsSubmicrometer-sized Presolar Grains

NanoSIMS Studies (II)NanoSIMS Studies (II)

Group 2 Group 1

Group 3

Group 4

Figure 1

1.0E-4

1.0E-3

17O

/16O

1.0E-4 1.0E-3

18O/16O

Semarkona

OCs

Orgueil

Murray

solar

sola

r

OC2M12

OR1

M8OR4

OC1

M16M20

M18

M17

OC3OR2

M13

M10

S-S21

Zin

ner et al., 2005

O in Presolar SpinelO in Presolar Spinel

NanoSIMS Studies (III)NanoSIMS Studies (III)

Isotopic homogeneity can be Isotopic homogeneity can be studied within micrometer-sized studied within micrometer-sized presolar grainspresolar grains

In most cases isotopic compositions In most cases isotopic compositions turned out to be homogeneousturned out to be homogeneous

Isotopic heterogeneities:Isotopic heterogeneities: TiC within graphiteTiC within graphite SiC from supernovaeSiC from supernovae

Isotopic Homogeneity within Presolar Isotopic Homogeneity within Presolar GrainsGrains

NanoSIMS Studies (IV)NanoSIMS Studies (IV)

28Si48Ti

min max

18O/16O17O/16O16O

16O 17O/16O 18O/16O

1 m

Sah-602-4

Standard grain

Mostefaoui et al., 2002

O in Presolar CorundumO in Presolar Corundum

NanoSIMS Studies (V)NanoSIMS Studies (V)

MurchisonSiC X grains

MainstreamGrains

-1000 -800 -600 -400 -200 0 200 400

d30Si/28Si (‰ )

-1000

-800

-600

-400

-200

0

200

400

d29S

i/28S

i (‰

)

NanoSIMSNanoSIMS, 44TiIMS3f

Besm

ehn

and

Hop

pe, 2003

Presolar SiC-XPresolar SiC-X

NanoSIMS Studies (VI)NanoSIMS Studies (VI)B

esmeh

n an

d H

opp

e, 2003

30Si/28Si28Si

min max

1 m

28Si 29Si/28Si 30Si/28Si

Presolar SiC-XPresolar SiC-X

NanoSIMS Studies (VII)NanoSIMS Studies (VII)

Most presolar minerals can be separated by Most presolar minerals can be separated by harsh chemical treatments from meteoritesharsh chemical treatments from meteorites

Does not hold for silicatesDoes not hold for silicates Silicates are the major constituent of O-rich Silicates are the major constituent of O-rich

dust around starsdust around stars First silicates discovered in an IDP in 2002 First silicates discovered in an IDP in 2002

(Messenger et al.); use of NanoSIMS was (Messenger et al.); use of NanoSIMS was essentialessential

O-isotopic mapping of slices of meteorites or O-isotopic mapping of slices of meteorites or IDPs with 100 nm lateral resolutionIDPs with 100 nm lateral resolution

Presolar SilicatesPresolar Silicates

NanoSIMS Studies (VIII)NanoSIMS Studies (VIII)

16O 17O 17O/16O

Acfer 094 Meteorite (Mostefaoui and Hoppe, 2004)

Presolar SilicatesPresolar Silicates

NanoSIMS Studies (IX)NanoSIMS Studies (IX)

Simultaneous information on Simultaneous information on mineralogy, structure, isotopic mineralogy, structure, isotopic compositions, and petrological compositions, and petrological context of presolar materialscontext of presolar materials

Preparation of thin sections of Preparation of thin sections of individual particles by ultra-individual particles by ultra-microtomy or FIB lift-outmicrotomy or FIB lift-out

Coordinated NanoSIMS-TEM StudiesCoordinated NanoSIMS-TEM Studies

NanoSIMS Studies (X)NanoSIMS Studies (X)

1

2

3

NRL, Carnegie Institution, and MPI Mainz, 2004, unpublished

Presolar SiC-XPresolar SiC-X

RIMS Studies (I)RIMS Studies (I)Zr in SiC mainstream grainsZr in SiC mainstream grains

Nicolu

ssi et al., 1997

90 92 94 96Zr isotope

-1000

-800

-600

-400

-200

0

200di Z

r/92

Zr

(‰)

91

Grain KJH-151

s-process path

RIMS Studies (II)RIMS Studies (II)

-400

-200

0

d90Z

r (ä

)

-400

-200

0

d91Z

r (ä

)

-200

0

d92Z

r (ä

)

-1000 -800 -600 -400 -200 0

d(96

Zr/94

Zr) (ä)

D12D6D3D2D1.5STU1.3U2

SiC grains

[Fe/H]=0solar

metallicity

1.5 M

Lessons from Zr:Lessons from Zr: Mainstream SiC grains Mainstream SiC grains

come from low-mass come from low-mass AGB stars, probably AGB stars, probably mostly 1.5–3 Mmostly 1.5–3 M; 5 M; 5 M can be excludedcan be excluded

A variety of conditions A variety of conditions are required to explain are required to explain the array of grain the array of grain compositionscompositions

Models do a good job of Models do a good job of explaining most of the explaining most of the data, but low data, but low 9696Zr grains Zr grains remain a difficultyremain a difficulty

Zr in SiC mainstream grainsZr in SiC mainstream grains

RIMS Studies (III)RIMS Studies (III)9999Tc in SiC mainstream grainsTc in SiC mainstream grains

Savina et al., 2004

RIMS Studies (IV)RIMS Studies (IV)Mo in SiC X grainsMo in SiC X grains

Pel

lin

et

al.,

1999

Although previously Although previously postulated, a new type postulated, a new type of nucleosynthesis was of nucleosynthesis was recognized in naturerecognized in nature

The neutron burst The neutron burst required is a natural required is a natural consequence of Type II consequence of Type II supernova explosionssupernova explosions

X-grains must come X-grains must come from Type II, not Type Ia from Type II, not Type Ia supernovae, as such a supernovae, as such a burst does not occur in burst does not occur in SN IaSN Ia

SummarySummary

NanoSIMS and RIMS have become well-NanoSIMS and RIMS have become well-established tools in presolar grain researchestablished tools in presolar grain research

Important breakthroughs:Important breakthroughs: Extension of isotope analyses to Extension of isotope analyses to

submicrometer-sized grainssubmicrometer-sized grains Study of isotopic homogeneity within Study of isotopic homogeneity within

micrometer-sized grainsmicrometer-sized grains Discovery of presolar silicate grainsDiscovery of presolar silicate grains Isotope analyses of the heavy elements by Isotope analyses of the heavy elements by

RIMS provided important input for a better RIMS provided important input for a better understanding of neutron-capture reactions in understanding of neutron-capture reactions in the grain’s parent starsthe grain’s parent stars