101: An Introduction to LA-ICP-MS

Lucas Smith Director of Business Development - Americas Content 66Zn+ E14-17 • What is ICP-MS? • Laser ablation vs other analytical techniques • Laser sources and selection • The importance of washout times • Fractionation effects • Application examples • Q&A What is Laser Ablation? • A laser ablates a solid sample & delivers material directly to the ICPMS for elemental analysis

• Eliminates dissolution step and most sample prep

• Maintain spatial resolution What is Laser Ablation & Why do we care?

• Rapid, sensitive multi-element detection at sub-ppm levels.

• Eliminates (most) labor-intensive sample preparation

• Can sample virtually any material (including liquids)

• Flexible method development

• High spatial resolution of microfeatures

• Sample mapping and depth profiling capabilities

• No contamination of reagents from digestion/dilutions steps Sample Analysis Sample Analytical Method Type Requirements SEM/Microprobe Laser Ablation techniques vs GDMS and OES Other XRF Techniques Spark Emission

Laser Ablation Non Full coverage Turnaround Bulk Spatial Depth Conducting Size/shape limits Detection - conducting What is Laser Ablation ICP-MS?

References: Hu et al, J. Anal. At. Spectrom., 2008, 23 & Eggins et al, Applied Surface Science 127-129 (1998) Laser Ablation System – Excimer Light Path Typical Set-Up

ICP-MS Make-Up Helium (or Argon) Sweep

Sample He

Trigger (Optional) LASER HelEx II Sample Chamber

Internal volume (cup)

Sample holder

Articulated gas inlet/outlet arm

• Evolution of Steve Eggins original ANU design

S. M. Eggins, L. P. J. Kinsley and J. M. G. Shelley, Appl. Surf. Sci., 1998, 129, 278–286. Typical used in Laser Ablation

Nd:YAG LASER 1064 nm

Nd:YAG LASER 2nd 4th Harmonic Harmonic 1064 nm 532 nm 266 nm

Nd:YAG LASER 2nd 3rd 5th Harmonic Harmonic Harmonic 1064 nm 532 nm 355 nm 213 nm

ArF Nanosecond pulse width 193 nm

Femtosecond lasers Fspulse width Wavelength & Coupling Efficiency

• Highly light transmitting materials (e.g. quartz) absorb little light under 300nm

• About 20% is absorbed at 266nm

• About 50% is absorbed at 213nm 266

• > 90% is absorbed at 193nm FRACTIONATION: When the elemental composition of the material measured at the detector is not representative of the sample’s true composition

High Low

Particle Size High Particle Size Low

PS Distribution High PS Distribution Low

Difference in Mass High Difference in Mass Low

Difference in Volatility High Difference in Volatility Low

Ideal Sample to minimize fractionation: Homogenous, high-density aerosol cloud consisting of small, similarly sized particles. Fractionation

Liquid Nebulization

Laser Ablation

Reference: D. B. Aeschliman, S. J. Bajic, D. P. Baldwin and R. S. Houk, High-speed digital photographic study of an inductively coupled during laser ablation: comparison of dried solution aerosols from a microconcentric nebulizer and solid particles from laser ablation, J. Anal. At. Spectrom., 2003, 18, 1008–1014 Analytical Implications Wavelength and Fractionation Laser Type Heating Effects Coupling Typical Particle Overall Efficiency with Size Fractionation Translucent Distribution Effects Samples

1064 nm High Very Poor Broad Poor

266 nm Moderate Poor Moderate Moderate

213 nm Low-Moderate Good Narrow Good

193 nm Low Excellent Very narrow Very Good

Femto Very Low Wavelength Very narrow Excellent dependent (in metallic samples) What does laser ablation look like? What Can Be Ablated? • Zircons & a variety of geological samples

• Ice Cores (climatology)

• Paper and ink ablation (forensics)

• Hair Samples (Pb, As & Sr measurement)

• Sunflower leaf

•

• Bio-analysis Teledyne Laser Portfolio

LSX-213 G2+

Analyte Pharos

Analyte Excite & High Energy Systems

Fusions CO2 & Diode Systems Iridia – The Evolution of Laser Ablation

• Purpose design for high speed imaging

• Dual Attenuation enables stable low energy for bio-imaging applications

• Dual software controlled polarizers for geo- imaging applications

• sample chamber for ultimate performance & flexibility Application Areas

• Earth Sciences • Minerals, toxic elements, zoning, U-Pb dating, coral, environmental record • Forensics • Glass, paint, plastic, metals, inks • Archeology • Ceramics, shards, bone, teeth • Pharmaceutical • Tablet powders and coatings • Metals • Alloys, precious metals, QC and defects • General Industrial Materials • Glass, quartz, silicon • Biological/Medical • Tissue (frozen or dried), bone, teeth Trace elemental analysis of stalagmite Zircon Geochronology

Chew et al, J. Anal. At. Spectrom., 2017, 32, 262

Agilent 7900 ICP-MS TDY PMI Analyte Excite with HelEx Spot size: 7um Scan speed: 20um/s Rep Rate: 45Hz

“With an acquisition time of less than 10 minutes per map (which can be decreased even further), there are few reasons to perform spot analyses on complex polyphase zircons other than when sensitivity is needed.” Elemental Distribution in Garnet

Large (> 5 mm) garnet porphyroblast from medium-grade metamorphic rocks from the South Carpathians (Romania)

48 min Acquisition Time 150Hz Rep Rate

• HelEx II & ARIS • Around 30ms transient peaks

• ICP-TOF-MS (TOFWERK)

Dr C Stremtan (Teledyne), Dr M Rittner (TOFWERK) Data interpretation: comparison to histology by overlaying a sequential HE-stained microtome slice

• Evaluation of links between cell-types and the nuclide, compound, or anti-body distribution made possible

Frank Vanhaecke, University of Ghent 3D Fly-Over of Concentration Image

T Van Acker, University of Ghent Zn in Mouse Small Intestine

• Cobalt Cell & Quad ICP-MS • HDIP Software

• Deparaffinized 5 µm sections of mouse small intestine villi • Pixel size of this image is 1 x 1 µm • Total image size 350 x 300 µm, 50µm • Spot size 1 µm, • laser rep rate 150 Hz, • energy density 0.44 J cm-2 • Pixel acquisition rate 50 pixels/sec (limited by ICP-MS software)

• 35 minutes to acquire data Amazingly Large Images • Zircon Grain • 3 um spot size @ 250 Hz

Zircon from the Ditrau alkaline massif • 4.7 Million Pixel 3D Images (Eastern Carpathians, Romania) • 2 hours to acquire on ICP-MS

• Mass: U238

• 7 Minutes acquisition time per layer

• 100 layers acquired

• Single laser shot per pixel

• Z 150 nm material removed

• 1.5 x 1.7 mm Cobalt – Engineered by Science

Three-Dimensional Reconstruction of the Tissue-Specific Multi-elemental Distribution within Ceriodaphnia dubia via Multimodal Registration Using Laser Ablation ICP-Mass Spectrometry and X-ray Spectroscopic Techniques. Stijn J. M. Van Malderen et Al, DOI: 10.1021/acs.analchem.7b00111 Our laser webinar series continues!

Laser Ablation 102: The Evolution of LA-ICPMS Laser Ablation 201: Applications of Laser Ablation & through Collaborative Science Data Reduction Strategies

Damon Green – VP of Marketed Technology Dr. Ciprian Stremtan (and Muffin) – Product Specialist