Dr Ciaran O‟ConnorLaser Ablation Sales Manager

Electro Scientific Industries Europe Ltd.

New Wave Research Division

University of Modena

29th May 2009

Novel Applicationsof LA-ICP-MS

www.new-wave.com

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Overview

What is Laser Ablation?

Why use Laser Ablation?

Which Wavelength?

Current solutions

Some Novel Applications

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What is Laser Ablation?

Laser Ablation is a solid sampling technique for use with:

– Inductively coupled plasma mass spectrometry (ICP-MS)

– Can also be used with Inductively coupled plasma optical emission spectroscopy (ICPOES)

A laser is used to generate a fine aerosol of sample particulate

A carrier gas (He) is used to transport the particles to the ICP

Particles are vaporised and ionised within the plasma

Ions are then tranported via electronic or magnetic lenses to a detector where they are counted.

Can be used on any solid sample!

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What is Laser Ablation?

He in ICP-MS

Hit a sample surface with a high irradiance beam (1µm to 1mm diameter)

Laser “couples” with the sample surface and creates a cloud of particulates

Transported to the ICP-MS for detection via a He/Ar carrier stream

Ablation Cell

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Laser Ablation ICP-MS

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What is Laser Ablation?

Short-pulse laser ablation is

characterised by a plume of energised

particles (visible to the naked eye)

Careful selection of resonator and

homogenising optics gives a flat beam

profile capable of depth profiling

Ablation made on

silicate glass using

UP193SS

Expanding plume of

ablated material

following ablation

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Why use Laser Ablation?

Samples can be difficult to digest PGE metals (Pt, Ir, Rh, Os, Pd) Loss of “volatiles” during digestion Plastics analysis for RoHS (e.g. Hg in PEEK)

Quick and efficient sample introduction Easy route from solid to ICP No need for dilution (no loss of sensitivity) Minimising potential for contamination from sample handling

High spatial resolution Spot size as low as 1 µm Ideal for „spatial chemistry‟, e.g. zonation in minerals

Can also do bulk analysis Breaking through the 1mm barrier High sample quantity for excellent sensitivity Large area for best homogenisation

Reduced interferences Oxide interferences removed almost entirely (no water, no acid) Interferences mainly from matrix (polyatomic and isobaric)

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Is Wavelength Important For My Application?

266nm

UP266MACRO4th Harmonic Solid State Laser (Nd:YAG)

213nm

UP2135th Harmonic Solid State Laser (Nd:YAG)

193nm

UP193FX or UP193SSArF Excimer (Gas Phase) or “pseudo 6th” Harmonic Solid State (Nd:YAG)

What wavelengths are available?

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Is Wavelength Important For My Application?

193nm

213nm

266nm

NIST610 NIST612 NIST614 NIST616

<1%

<1%

<1%

<1%

<1%

<1%

<1%

<1%

13%

<1%

1.5%

24%

Percentage Transmittance

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266 nm 213 nm 193 nm

Tree Rings, Biological Tissues, Plastics, Soils, Air Filters, Metals

Ceramics, Teeth, Coral, Glasses, Otoliths

Fluid Inclusions, Gems, Thin

Sections, Geo samples

Is Wavelength Important For My Application?

Highly coloured or non-reflective opaque materials can be analysed

by all wavelengths (e.g. NIST610)

Pale materials required low-UV (<213nm)

Transparent and colourless materials require deep-UV (193nm)

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266 nm 213 nm 193 nm

Tree Rings, Biological Tissues, Plastics, Soils, Air Filters, Metals

Ceramics, Teeth, Coral, Glasses, Otoliths

Fluid Inclusions, Gems, Thin

Sections, Geo samples

Is Wavelength Important For My Application?

Lower wavelength leads to smaller “particle size distribution”

Improved transportation to ICP

More fully vaporised and ionised within ICP

Higher sensitivity

Less Fractionation

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What is Fractionation?

Fractionation is a change in the measured ratio of isotopes compared to their true ratio

Elemental fractionation is the change in measured relative concentration between different elements (e.g. Cu:Zn, U:Th)

Isotopic fractionation is the change in measured relative concentration between isotopes of the same element (e.g. 206Pb:208Pb)

Can be caused:

At the ablation process

During the transport process

Within the plasma

Fractionation is reduced when the particles size distribution (PSD) is lower

Use of lower wavelength (e.g. 193nm) reduces the PSD

Use of shorter pulse width reduces the PSD

Current Solutions…...

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Laser Ablation – Family of Products

UP193SS

Deep UV in a bench-top solid state laser ablation system

UP193FX

Deep UV, short pulse excimer laser ablation system

UP213

General purpose UV in a bench-top solid state laser ablation system

UP MACRO

Large spot sizes at 266nm for bulk analysis, ultra-trace ICP-MS and ICP-OES

MIR10

Mid-infra-red laser heating and fusing

MicroMill

Precision milling tool for solid sample removalUP193FX

UP213

UP MACRO

MIR10

MicroMill

UP193SS

Some Novel Applications…...

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Forensic

Glass FragmentPaintHairGun Shot ResidueInkIdentification of “fakes”

• Drugs• Microchips• Golf Balls

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9mm line width

No fracturing

Hair Analysis

Single strand of hair

(67µm wide, 25µm hole)

Forensic/Archaeological analysis of

hair

Toxicological studies

Isotope ratio studies

Exposure studies (occupational,

environmental, anti-terrorism etc.)

Can also do growth profiling (scan

along length of hair)

Also useful for fingernails or

biological tissue

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Fingerprinting of Paint – Depth Profiling

Strategy 1:

Ablation of a single spot on sample surface

Signal changes with depth

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Fingerprinting of Paint – Depth Profiling

Strategy 2:

Line scan on the side profile of paint

fragment

Steady state signal for each layer

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Glitter™ Standards window

Distribution of refractive index (RI) values

FBI database of flat glasses, 1964 to 1979

Distribution of refractive index (RI) values

FBI database of flat glasses, 1980 to 1997

There is less variability in the

optical and chemical characteristics

of modern glass

Traditional techniques such as

refractive index discrimination is

becoming less effective

Glass Analysis

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The major constituents of clear glass are typically very similar

Differences may be found at trace levels < 100 µg/g (< 0.01%)

Glass Analysis

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1831

620

621

A, B,& C

Sheet Glass

Flat Glass

Container Glass

Headlamps

Glass Analysis

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Environmental

Air ParticulatesSoilPlant TissueTree Rings

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Atmospheric PM10 Particle Monitoring

Monitoring stations set up nationally

PM10 particles collected on quartz filters

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9mm line width

No fracturing

Analysis of particulate on

filter paper using 266nm

Nd:YAG

Able to resolve different

components of aerosol

Higher throughput than

solution analysis

Overcomes selectivity of

leaching methods

This study used to determine

Pb isotopic fingerprint of

PM10 particulate across the

UKCourtesy of Matt Horstwood, Steve Noble (NIGL, Keyworth) & Steve Smith (ERG, Kings College)

Atmospheric PM10 Particle Monitoring

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Atmospheric PM10 Particle Monitoring

2001 2010(projected)

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Atmospheric PM10 Particle Monitoring

Comparison with world-wide data

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Soil Pellet Bulk Analysis

Element Mean Concentration (ppm) %RSD Certified Concentration (ppm)

Cr 186 1.5% 195

Cu 36.2 3.6% 46.4

Cd 11.8 7.8% 14.6

Hg 0.21 3.7% 0.25

Pb 45.1 10.7% 57.2

Pressed powders are known for their heterogeneity

Use a laser ablation system with a large beam diameter to average out heterogeneities

UP266MACRO – 610 micron x 610 micron

Scan the beam in a long line to ablate as large an area as possible

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Archaeology& Conservation

CeramicsBone/TeethTissueHairRestorationInk/Documents

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Art Restoration

Must know the composition of materials before restoration Profiling with LA-ICP-MS gives direct information on layer composition

Fresco from roof of the Opera

House in Ljubljana, Slovenia

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Art Restoration

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Art Restoration

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Biological & Clinical

Tissue AnalysisElectrophoresis GelsToxicology

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Imaging of Elements and Proteins in Brain Tissue

24Mg

27Al

57Fe

63Cu66Zn β-Amyloid (153Eu)

Multiple line scans combined

to create elemental “maps”

By labelling proteins with antibodies that

have been tagged with Eu it is possible to

image a protein distribution by LA-ICP-MS

Hutchinson et al. Analytical Biochemistry 346 (2005)225-233

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LA-ICP-MS shows elemental

distributions in bone samples

Facilitates the study of

elements in the mineralization

zones of bone tissue

Resolution shows La occurs

only in mineralization zones

LA-ICP-MS used to examine

how metallo-drug compounds

interact with different types of

bone tissue to determine the

long term fate in the body

Acknowledgement

A.G. Cox1, J. Denton2 and C.W. McLeod1

1Centre for Analytical Sciences, University of Sheffield 2Laboratory Medicine Academic Group, University of Manchester

Profiling of La-drug Fate in Human Bone Tissue

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Oceanographic

CoralsFish ScalesOtolithsForamineferaOcean Geology

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It is possible to differentiate

daily environmental events from

the initial larval stages to

adulthood

Each day a new layer of

biogenic carbonate is formed

Each layer is 4µm to 20µm wide

Within these layers is locked the

environmental chemistry of the

fish

Chronological Exposure to Elements in Fish Otoliths

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Chronological Exposure to Elements in Fish Otoliths

www.esi.com 39Hathorne, E.C. et al, G3, 2003, (4), # 12

Ablation of Foraminifera

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LA-ICP-MS effective for isotope ratio and elemental analysis at concentration ranges from < 1ppb

LA-ICP-OES effective for a concentration range between < 1ppm to %. It is particularly good at handling heavy plasma loading

The micro-destructive nature of laser ablation spectrometry preserves sample integrity

It is a direct, solid sampling technique

Laser Ablation Spectrometry is particular useful when analyzing samples that are difficult to digest or when there is very little of the sample available

Laser Ablation Spectrometry is FAST

Summary of Laser Ablation