Zurich, 17.03.2011 1

Die Bedeutung von

Spurenelementen für die

Rekonstruktion der Vergangenheit

und die Gestaltung der Zukunft

Detlef Günther

Laboratory of Inorganic Chemistry,

ETH Zurich, CH-8093 Zurich, Switzerland

◊

Begin of Atomic Spectroscopy 1960

Bunsen und Kirchhoff

Robert Wilhelm Bunsen

geb. 30.3.1811 in Göttingen

gest. 16.8.1899 in Heidelberg

Robert Gustav Kirchhoff

geb. 12.3.1824 in Königsberg

gest. 17.10.1887 in Berlin

Zurich, 17.03.2011

◊

First Results of Analytical Atomic

Spectroscopy*

Element Discoveries*

1861 Rb, Cs Bunsen, Kirchhoff

1861 Tl Crooks

1863 In Reich

1868 He im Sonnenspektrum Lockyer

1875 Ga Boisbaudran

1880 – 1900 Seltene Erd-Elemente

1894 Ar Ramsay

Based on measurements of spectral lines

Ed. 2008

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4

Today‟s Major Players

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Contents

Introduction into Trace Element Analysis

Applications:

Ore Formation and Gold Analysis

Climate Studies on Titanium

Provenance on Traces and Isotopes

Future directions

Research on Nanoparticles

Summary

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Archeometry

Industry

Medicine Biology

Forensic

Geology

Material

Science

Analytical

Chemistry

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Trace Element Analysis

Requirements

- Multielement

- Fast and reliable

- In situ

- Quantitative

- Precise and accurate

- High spatial resolution

- Sensitive

- No sample preparation (no sample alteration)

Applications

- Environmental pollution

- Earth formation processes

- Industry (process control)

- Climate archive analysis

- Characterization of new materials

- Solar system analysis

- Forensic studies (past and present)

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Extraction

Digestion

„ ‟ex-situ

destructive

Selectivity

Sensitivity

Concentration

bulk ( voxel size)

X-Rays

Laser

„in ‟-situ

non-destructive

Selectivity

Sensitivity

Concentration

Structure

Speciation

micro to bulk ( beam size)

Particle Beams (e , H , ...)- +

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Today Micro

Nano

Sample Mass

“Tomorrow”

Spatial resolution

fg

m mg

nm

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Cycle of Analytical Chemistry Research

Application

Improved

Understanding

ofTrace Elements

Method Development

New Instrumentation

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Instrumentation for Trace Element and Isotope Analysis

Sample prep ICP-MS instruments Laser and XRF equipment

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Laser Ablation Inductively Coupled

Plasma Mass Spectrometry

Houk RS, J Anal At Spectrom,

(2003), 18, 1008-1014

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Trace Element Detection Limits in Solids

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Trace Element Analysis

Geology – Ore Exploration

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Bajo de la Alumbrera (Argentinien):

Cu-Au-Ore Deposite

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Porphyry-copper ore…vein network

Porphyry

Cu-Au ore:

Parkes,

NSW

2 cm

Berlin 9th of November 2009 17

Bildbreite ca

3cm

Cavnic,

Rumaenien

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40 m crater

hyper-

saline

liquid

(brine)

vapour

Host Quartz with Inclusion Trails

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Quantification Strategy for

Fluid Inclusions using

LA-ICP-MS

Shepherd et al., Audetat et al., Heinrich et al., Ulrich et al.

20

Fluid Inclusion Analysis

Günther et. al. 1998 Zurich, 17.03.2011

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Reconstruction of the Gold Budget in an Ore

Deposite from 20 m Inclusions

T. Ulrich, D. Günther, C.A. Heinrich, Nature, vol. 399, p. 676-679

Au/Cu = 1.1x10-4

Determination of the Ore Quality

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Task:

Determination of the precious metals

to concentrations as low as 20 ng/g

Sample Preparation Steps

23 Zurich, 17.03.2011

+

slag

Crucible

Separation

and mould

Direct solid

sampling analysis

◊Grinding

◊Acid digestion

◊(HCl)

◊Te Coprecipitation

◊Filtering and

◊washing

◊Digestion of

◊filter paper

◊Solution

◊for analysis

◊Heating (1100ºC)

◊with oxidizing agent

◊Heating (1300ºC)

◊to remove impuririties

◊Digestion

◊Solution

◊for analysis

Button with

PGMs B

A ◊Traditional

◊approaches

+

Sample

Flux

Furnace

◊1200ºC

Analysis Cycle of PGE„s

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450 mm

70 mm

40 mm

Ablation Cell Design

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SARM 65 in mg/kg

SARM 66 in mg/kg

Results using fs-LA-ICP-MS

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Location and Map Profile

Chambers found in an

ore mine (Ag, Pb, Zn)

which is 100 yrs old

Samples from three

different levels

Espadas is known for

many years, but the

others were discovered

only in 2002

Explored by LaVenta

By Paolo Forti

28

Espadas

crystals up to 2m Thermal springs

grown during last 17 yrs

Sample Location

La Venta La Venta

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Fluid Inclusions

Small compartments of

liquid enclosed in

mineral

during crystal growth

In fractures

Stored characteristics of

forming liquid, important

for geologists

As old as the crystal

1 mm

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Results for Espadas

Na

Mg

K

Sr

Pb

1 cm

1 cm

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31

Trace Element Analysis

Climate

32

Progressive Development of Sediments

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33

Maya Societal Evolution

0 20

km

Yaxha

SacnabPet én-ItzaPerdida

Sacpuy

Quexil

Pet énxil

Salpet én

Macanch é

N

Tikal

Atlantic Ocean

Gulf of Mexico

Pacific Ocean

Caribbean

20 º N

10 º N

100 º W 90 º W

Pet én

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Berlin 9th of November 2009 34

Sampling and Sample Preparation

Processes

35

Working Hypothesis

+

= †

x

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36

ODP Site 1002: The Cariaco Basin

Haug et al., Science, 2001

Younger

Dryas

(YD)

Holocene

'thermal maximum'= Laminated Sediment

= AMS 14C dates

0 1 2 3 4 5

0.1

0.2

0.3

0.4

1060

2340

3460

4995

6720

11081

99508060

0 1 2 3 4 5 6

0

5

10

15

depth (m)

Ag

e (

ca

len

da

r k

ilo

ye

ars

BP

)

4

3

2

1

298

= AMS 14C dates

depth (m)

Tit

an

ium

(%

)

Iro

n (

%)

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37

Maya Societal Evolution

Chacmol - Maya Rain God

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Sediment Analysis

Age (calendar ka BP)

25

15

Tit

an

ium

(c

ps

)

5

'Litt le Ice Age''Medieval Warm Period'

0 0.5 1 1.5 2

~AD 200’s:

Pre-Classic

abandonment

~AD 800’s:

Terminal Classic

Collapse dry

wet

Haug et al.,Science, 2001Zurich, 17.03.2011

39

-X-ray Fluorescence

Rh-Target

HV Heating

X-ray tube

Liquid nitrogen

Capillary optics

Sample

Detector

X, Y, Z - Table

40 m resolution needed for monthly climate record

over the last 2000 years

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40

-XRF Instrumentation and Developments

Cooling stage for wet slabs

120 cm sample placeable in the sample room

Online measurements (days)

Max. resolution 50 um:

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41

Impact of Climate

dry

wet

on Maya Civilization

810 860 910 760

Science 2003 Zurich, 17.03.2011

42

Collaps of the Maya Civilization

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43

Other possibilites:

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44

Trace Element and

Isotope Analysis

Provenance Studies

Synthetic or Natural?

45

Provenance Studies on

Gemstones

Requirements:

quasi non-destructive

sensitive

multielement

major,minor and traces

Questions:

Natural or synthetic?

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46

Quasi “Non-destructive”

Fingerprinting

1 2 3

60 nm depth/pulse

120 m diameter

20 pulse

per analysis

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Fingerprinting of Sapphires

Fe

Cr

Ga

group 1group 2

group 3

group 4

group 5

Groups: Tansania, Sri Lanka, Cashmir, Burma, Thailand

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Andesine

48 Zurich, 17.03.2011

49

Fingerprint Andesin (Tibet)

Andesine (Tibet)

0.001

0.01

0.1

1

10

100

1000

10000

100000

1000000

Li B

Mg Al K

Sc V

Mn

Co

Cu

Ga

Rb Y

Nb

Cs

La Pr

Sm Eu

Tb

Ho Hf

Bi U

Elements

Co

ncen

trati

on

in

pp

m

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Similarity between Tibet & Mongolia

Andesine (Tibet/Mongolia)

0

0.5

1

1.5

2

2.5

3

Li

B

Mg Al

K

Sc V

Mn

Co

Cu

Ga

Rb Y

Nb

Cs

La

Pr

Sm Eu

Tb

Ho Hf

Bi

U

Elements

Tib

et/

Mo

ng

olia

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◊Detector

Magnet

ESA

Ion

Optics

Plasma

Chamber

52

27.07.2009 Cu in Andesines

-1.50

-1.00

-0.50

0.00

0.50

1.00

1.50

2.00

Tibet6 Tibet5 Mongolia Tibet12 Tibet11

Delt

a f

rom

NIS

T610

1st run

2nd run

65/63 Isotope Ratio Measurements

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Peru - Gold Deposits and Objects

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EB 15-052.03 Ebnöther Collection

flying shaman nose ornament

Composition

80.4

80.3

70.8

17.8

26.1

17.9

2.9

1.6

1.5

0 20 40 60 80 100

pendant

connecting

ring

suspension

ring

c [wt%]

Au Ag Cu

Determined element concentrations (mg/kg)

Ti Mn Fe Zn Pd Cd Sn Sb Te Pt Pb Bi

Suspension ring 1.45 1.22 - 49 43 - 1.23 0.51 - 2039 4.6 0.40

SD - 0.19 - 4 4 - 0.19 0.10 - 13 1.5 0.03

Connecting ring 2.15 9.3 328 34 56 0.42 1.3 3.31 2.58 2293 43 1.8

SD 0.12 4.2 134 10 15 - 0.5 1.38 0.04 548 10 0.3

Pendant 2.51 6.7 320 26 57 0.47 1.20 2.68 1.58 2388 36 1.49

SD 2.14 1.5 80 4 4 0.14 0.15 0.20 - 117 6 0.05

Analysis of Gold Artifacts

50 m

LA: ns-LA (266 nm)

10 Hz, 50 m, 10.2 J cm-2

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Future Research

~12„000 km

~10 cm

>100 nm 10-9 10-9

Nano: (gr.νᾶνος; dwarf)

◊50 nm

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Man kann sich einer

einmarschierenden Armee

entgegenstellen,

aber nicht einer Idee,

deren Zeit gekommen ist

Victor Hugo

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Applications

Sunscreens (ZnO, TiO2)

UV protection in coatings (ZnO, TiO2)

Flowing agent (SiO2)

Mechanical properties of car tires (carbon black)

Bioactive implant materials (Calcium phosphate)

Magnetic separation (magnetic cobalt or iron)

Antimicrobial coatings (Ag)

Solar cells (semiconducting materials, TiO2)

Li-Batteries (LiFePO4)

…

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Flame Spray Synthesis

Patents:

W. J. Stark et al., US2006229197 (A1).

W. J. Stark et al., US7879303 (B2).

W. J. Stark et al., US7211236 (B2).

W. J. Stark et al., US2008268246 (A1).

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Single Particle Introduction

Ar Ar

Ca(NO3)2 (aq) He

Micro-

Dispenser 1,2

Adapter

Fall tube ◊Ar

MS

Plasma torch

Ar Ar

1. Gschwind, S., Flamigni, L., Koch, J., Borovinskaya, O., Groh, S., Niemax, K. & Gunther, D., Submitted to: J. Anal. At. Spectrom.

(2010).

◊1 ◊2 ◊3 ◊4

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Nano Particle Materials

C. C. Garcia, A. Murtazin, S. Groh, V. Horvatic and K. Niemax, Journal of Analytical Atomic Spectrometry, 2010, 25, 645 - 653. A. Murtazin, S. Groh and K. Niemax, Journal of Analytical Atomic Spectrometry,

2010, 25, 1395-1401.

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Single Nanoparticle Analysis

Limits of Detection in the order of 15-20 nm

Signal duration less than 0.5 ms

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Summary

Trace elements and

isotope ratios elucidate

the past, present and

contribute to shape the

future

Higher sensitivity will be

required to unravel

more processes on the

required atomic level

Topics:

Climate, batteries, catalysts,

fuel, nanomaterials, star

dust, minerals, solar cells,

waste water, food, cancer

treatments, dating of rocks

and sediments, authenticity

of materials,

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Trace Element & Micro Analysis (ETH-Zurich)

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Acknowledgements

Group for Trace Element and Micro Analysis

Matthias Fricker

Sabrina Gschwind

Olga Borovinska Dr. Bodo Hattendorf

Karin Birbaum Dr. Joachim Koch

Robert Kovacs Dr. Rolf Dietiker

Gisela Fontaine Dr. Helmar Wiltsche

Reto Glaus

Tatjana Egorova

Luca Flamingi

Robert Brogioli

Hao Wang

Ladina Dorta

Kathrin Hametner

Beat Aeschlimann

Collaborators

Markus Kalberer (ETH Zürich)

Annemie Bogaerts (Uni Antwerp)

Roland Hergenröder, Kay Niemax (ISAS Dortmund)

Thomas Lippert (Paul Scherrer Institut, Switzerland)

David Hahn (University Florida, USA)

Charles Lienemann (Lyon)

Funding ETH Zürich

Swiss National Science

Foundation

CETAC Technologies

Spectro Analytical Instruments

Perkin Elmer/Sciex

NITE Crime EU Network

Umicore (Liechtenstein)

Philips (NL)

BASF (Germany)

Marie Curie Fellowship EU

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◊2010.05.03 ◊66

Vielen Dank für Ihre Aufmerksamkeit