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Forensics applications of X-ray fluorescence microscope

Article  in  Powder Diffraction · June 2008

DOI: 10.1154/1.2951678

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 FORENSICS APPLICATIONS OF X-RAY
FLUORESCENCE MICROSCOPE.

Sergey Mamedov, Jon Goldey, George Setola, Andrew Whitley

Horiba Jobin Yvon Inc. Edison, NJ, USA

DXC 2008, Denver August 4-8 2008

 Overview

9Why we need X-Ray Fluorescence Microscope?

9Gun Shot Residues
9Fingerprints
9Counterfeit products/devices
9Museum and archeological objects
9Trace elements analysis
9Summary

DXC 2008, Denver August 4-8 2008

 Why we need XRF Microscope?

Bulk XRF analysis

• Traditionally, routine XRF analysis has been a bulk/macro

technique
• Spot sizes typically several mm in diameter
• Good for bulk powders, liquids, solids
• Excellent quantitative data – ppm level

How to transform this into a microscopic

technique?

DXC 2008, Denver August 4-8 2008

 Why we need XRF Microscope?
Mono- Poly-capillary
Collimator capillary

X-ray Total
convergence reflection
device

Minimum High energy: 30 µ

About 10 μ 10 μ Low energy: 90 µ
beam size
Divergence of None Small Large
X-ray (Parallel rays) (Almost parallel rays)

Intensity ratio 1 20-100 1000

DXC 2008, Denver August 4-8 2008

 Why we need XRF Microscope?
Influence of uneven surface
Focal point Focal point ± 3 mm Focal point ± 5 mm
±0
± 3 mm
Mono-capillary
± 5 mm
Poly-capillary

±0
± 3 mm
± 5 mm

W-Lα mapping
DXC 2008, Denver August 4-8 2008
 Why we need XRF Microscope?
Comparison between Mono- and Poly-capillary at focal point

Low energy High energy

W-M (1.77keV) W-La (8.41keV)
Low energy
High energy

capillary
Mono-
Poly-capillary

Low energy
High energy

DXC 2008, Denver August 4-8 2008

 Sampling geometry

X-ray Guide Tube

Camera

Detector

mirror
sample
Y
X
Transmission detector

DXC 2008, Denver August 4-8 2008

 Dual vacuum chamber

Non vacuum Partial vacuum Full vacuum

: Vacuum
Detector X-ray tube

Switchable

Sample chamber

Liquid, powder Higher sensitive to

biological or wet sample light elements (Na,Mg,Al,…)

DXC 2008, Denver August 4-8 2008

What we can Analyze?

Pb
Al

hollow-point bullet

DXC 2008, Denver August 4-8 2008

 Gun Shot Residues
• Material deposited on a surface as a direct result of
discharging a weapon
• Includes bits of bullet, jacket, cartridge case, gunpowder
and primer residue

Our suspects

DXC 2008, Denver August 4-8 2008

 What we are looking for?
Initiator Fuel/Frictionator Oxidizer

Lead (Pb), Calcium (Ca) Antimony (Sb) and Barium (Ba)

+
Copper (Cu), Iron (Fe), Potassium (K), Zinc (Zn), Nickel
(Ni), Silicon (Si), Aluminum (Al), Sulfur (S), Phosphorus (P)
(rare), Chlorine (Cl)

Clusters
Sizes of GSR vary from submicron to hundreds of microns

DXC 2008, Denver August 4-8 2008

 Gun Shot Residues

White Light and Fluorescence Images

CS-16-500 + Short Pass Filter SP540 + orange barrier filter

DXC 2008, Denver August 4-8 2008

 Gun Shot Residues

Chemical images of Ca, Fe, Cu, Ba and Pb

100 μ capillary

Ca Kα Fe Kα Cu Kα Ba Lα Pb Lα

29.2 mm
DXC 2008, Denver August 4-8 2008
Gun Shot Residues
Cu distribution
100 μ capillary

10 μ capillary

29.2 mm
X-ray transmission image

1 mm
DXC 2008, Denver August 4-8 2008
 Gun Shot Residues
10 μ capillary
Optical image X-ray transmission
image Cu Kα Pb Lα

Ca Kα Fe Kα Ba Lα

~ 40 μ

1 mm ~ 20 μ
DXC 2008, Denver August 4-8 2008
 Gun Shot Residues

Sum Spectrum

D ~ distance between
firing point and target
Ca

Pb
Fe
Pb
Fe Pb
Ca Pb

4 5 6 7 8 9 10 11 12 13 14
Full Scale 14270 cts Cursor: 8.256 (2564 cts) keV

DXC 2008, Denver August 4-8 2008

 Fingerprints
Ag-containing TX – X-ray transmission image
physical developer + KI

DXC 2008, Denver August 4-8 2008

 Fingerprints
on fabric.

Vacuum deposition of

1. thin layer of gold (Au)

2. thick layer of zinc (Zn)

Rh Zn

fabric

DXC 2008, Denver August 4-8 2008

Counterfeit products/devices

Vendor 1

Vendor 2

DXC 2008, Denver August 4-8 2008

 Counterfeit products/devices

Vendor 1

Vendor 2 Cr Mn Pb

DXC 2008, Denver August 4-8 2008

 Counterfeit products/devices

Counterfeit Original

DXC 2008, Denver August 4-8 2008

Counterfeit products/devices
Toner

DXC 2008, Denver August 4-8 2008

 Museum and Archeological Objects

Au

Pb Hg
DXC 2008, Denver August 4-8 2008
 Trace elements analysis
and
Harmful elements

Lead (Pb) Pigment, ink, solder Cadmium (Cd)

Paralysis of human body and battery Effects nervous
effects brain system and liver

Coloring material for battery

plating, vinyl chloride and plastic
Mercury (Hg)
Minamata disease Chromium (Cr)
hearing problems
Lung cancer Plating, matches, colors,
Electrode, Battery, fluorescent light pigment and film
dental material, pigment and catalyst

DXC 2008, Denver August 4-8 2008

 Trace elements analysis
High concentration of Pb is detected from rubber caterpillars.

Caterpillar (right)
Pb 3000ppm

29.696 mm

Caterpillar (left)

Pb 52ppm

Optical image Pb-Lα

DXC 2008, Denver August 4-8 2008

Trace elements analysis
Pb 300-800 ppm

DXC 2008, Denver August 4-8 2008

 Trace elements analysis
Analysis of a relay contact

Cd free products

Conventional
products

Transmission image Cu + Cd + Br Composite map

DXC 2008, Denver August 4-8 2008

 Trace elements analysis
Paint

Mn Zn Zn Paint 1200P6 Ca Spectrum25

Fe Ti

Ti
Ca
Fe

Ti Zn Al
Ti
Fe Mn Zn Zn
Ti Fe Zn
P Fe
Mn
0 5 10 15 20 25 30 35 40
0 2 4 6 8 10 12 14 16 18
Full Scale7865cts Cursor: 3.614 (1204cts) keV
Full Scale522cts Cursor: 11.913 (26cts) keV

DXC 2008, Denver August 4-8 2008

 Trace elements analysis
Glasses

Elem. Intensity[cps/mA] Formula Mass[%] Molecule[%]

11 Na 189.36 Na2O 17.91 19.37

13 Al 115.54 Al2O3 1.21 0.8

14 Si 10933.98 SiO2 63.25 70.57

19 K 190.43 K2O 0.26 0.19

Pb Zn Glass 1200 P6
Si
20 Ca 290.19 CaO 0.37 0.44

22 Ti 582.86 TiO2 0.94 0.79

30 Zn 20713.7 ZnO 5.78 4.76

Pb
82 Pb 10882.53 PbO 10.28 3.09
Pb

Zn

Na Pb Pb
Ca
Ti Pb
Zn Al K Ti Pb

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Full Scale 1404 cts Cursor: 7.991 (16 cts) keV

DXC 2008, Denver August 4-8 2008

 Trace elements analysis

Fe Cr Fe + Cr Cu

DXC 2008, Denver August 4-8 2008

 Trace elements analysis

Mouse Liver

Unexpected high concentration of Fe is found

Ca Kα Fe Kα

Scanning range 23mm×23mm

DXC 2008, Denver August 4-8 2008

 Summary

•EDXRF is non-destructive method

•EDXRF does not require sample preparation
•EDXRF provides information about elemental composition of the object
•EDXRF microscope has
9high sensitivity with detection limit up to 5 ppm
9high spatial resolution which will allow to identify of individual
Gun Shot Residue particles, counterfeit object and devices
9quantitative analysis
• EDXRF can reliably be used to collect large area images of sample

DXC 2008, Denver August 4-8 2008

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732-494-8660 ext 284 sergey.mamedov@jobinyvon.com

DXC 2008, Denver August 4-8 2008